TW201144264A - Photoacid generator, method for manufacturing the same, and resist composition comprising the same - Google Patents

Abstract

There are provided a photoacid generator represented by the following 1, a method for manufacturing the same, and a resist composition comprising the same. wherein in the formula 1, Y represents any one selected from the group consisting of a cycloalkyl group having 3 to 30 carbon atoms, and a cycloalkenyl group having 3 to 30 carbon atoms; Q1 and Q2 each independently represent a halogen atom; X represents any one selected from the group consisting of an alkanediyl, an alkenediyl, NR', S, O, CO and combinations thereof; R' represents any one selected from the group consisting of a hydrogen atom and an alkyl group; n represents an integer from 0 to 5; and A+ represents an organic counterion. The photoacid generator can produce, at the time of exposure, an acid which has a low diffusion rate, has a short diffusion distance, and exhibits an appropriate of degree of acidity so that the line width roughness (LWR) characteristics can be improved.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoacid generator, a method for producing the same, and a photoresist composition containing a photoacid generator. More particularly, the present invention relates to a photoacid generator capable of generating an acid upon exposure, the acid having a low diffusion rate, a short diffusion distance, and exhibiting an appropriate acidity to make the line brother roughness ( Line width roughness ; LWR) characteristics can be improved, and the dissolution in a solvent such as pure water used in the process can be controlled, and a method for producing a photoacid generator, and a photoresist composition containing a photoacid generator . [Prior Art] With the replacement of the micro-processing method using photolithography, a photoresist having a higher resolution is required, and a chemical-amplified photoresist has been developed. Such a chemical type resist composition (e.g., a coffee resist resist composition) contains a photoacid generator. The photoacid generator in the chemically amplified photoresist composition is an important element which imparts excellent sensitivity to the chemically amplified photoresist and the photoresist composition in terms of resolution, LWR, sensitivity and the like (four). Therefore, a chemically enhanced (four) touch composition for the study of various types of photoacid generators. In addition, they have appropriate properties. In other words, they have been used as photoacid generators to improve the acid recording. The compounds have been modified and tested for cations, and the sensibility and sensitivity of ___, In t^,, 201144264 38471pif, studies to improve the properties of chemically amplified photoresists by modifying the anion portion of the photoacid generator are still insufficient. Based on the experimental data reporting that the anionic moiety can exert a greater influence than the cationic partial properties, which substantially alters the properties of the photoresist composition, the new invention relates to the anionic portion of the recently implemented photoacid generator. In addition, the demand for photoacid generators which can adjust the permeability while reducing the acid diffusion rate increases. In addition, recent sources of chemically amplified photoresists require even shorter wavelengths than the g-line or i-line regions that are commonly used, and are therefore directed to the use of extreme ultraviolet radiation, KrF excimer laser light, ArF excimer laser light, and extreme ultraviolet light. (EUV) Kodak, X-ray and electron beam lithography were studied. In particular, since the exposure process is performed using pure water in the immersion ArF method, the photoresist composition used in such an immersion ArF method needs to have the following characteristics: light contained in the photoresist composition The acid generator or the acid produced from the photoacid generator does not dissolve into pure water. SUMMARY OF THE INVENTION An object of the present invention is to provide a photoacid generator capable of generating an acid upon exposure, the acid having a low diffusivity, a short diffusion distance, and exhibiting an appropriate acidity to achieve a line width roughness (LWR) The characteristics can be improved, and the dissolution in a solvent such as pure water used in the process can be controlled. In order to achieve the above object, according to an embodiment of the present invention, a photoacid generator represented by the following formula 1 is provided: 6 201144264 / ιριι [Formula 1]

Μ ?1 H2

A+H'C 〇q2 In Formula 1, Y represents any one selected from the group consisting of a fluorene group of 30 to 30 carbon atoms and a bad group having 3 to 30 carbon atoms; QA Q2 Each independently represents a halogen atom; χ represents any one selected from the group consisting of alkanediyl, banyl, NR, S, hydrazine, CO, and combinations thereof, and RI is not represented by a hydrogen atom. And any one selected from the group consisting of alkyl groups; η represents an integer from 0 to 5; and A+ represents an organic relative ion. According to another embodiment of the present invention, there is provided a method of producing a photoacid generator comprising the first step of dissolving a compound represented by the following formula 8 in a solvent, and reacting the solution with a reducing agent to obtain a formula 6 a compound; a second step of reacting a compound represented by the following formula 7 with a compound represented by the following formula 6 in the presence of a basic catalyst to obtain a compound represented by the following formula 4; and a third step of: The compound shown is subjected to a substitution reaction with a compound represented by the following formula 5, and thereby a compound represented by the following formula 1 is obtained. 7 201144264 38471pif [Formula 8] M+ O 〇2 [Equation 6] o m. -〇441hoh \\ I O 〇2 [Equation 7] 〇5~~fx)-

[Formula 4] [Formula 5] A+Z- [Formula 1] a+-o-^-61-c2-c2~〇. II I 〇〇2 In Formula 1, Formula 4, Formula 5, 々β-alkyl, In the formula Q7 and the formula 8, R6 represents that the target #5 independently represents a halogen atom 丨Y represents an observation group of $3 to 3 carbon atoms and a radical having 3 to 3Q carbon atoms. Among the ethnic groups, X is the one selected from the group consisting of the following groups: Hyun Erji, Fu Erji, Qi, s, 〇, C〇 and combinations thereof; R, hydrogen Atom and a base; η represents an integer from 〇 to 5 8 201144264 and A+ represents an organic relative ion. It is selected from the group consisting of: u+, Na+, and κ+; and z_ represents any one of the following groups of ions: (〇s〇2CF3) I. (0S02C4F9 )- > (〇S〇2C8F17)- > (N(CF3)2)- ' (N(C2F5)2)- ' (N(C4F9)2) ^ (C(CF3)3)- , , (C (C2F5)3)- ^(C(C4F9)3)- 'F- > cn-, Br-, I-, BF4" AsV and pF6. Substituting another embodiment of the invention to provide a chemically amplified photoresist A composition comprising a photoacid generator as described above. The invention will be described more hereinafter. The terminology of the specification of the present invention is defined as follows. Unless otherwise specifically stated herein, a halogen atom means Among the constituent groups, the m and the angstroms are selected. Unless otherwise specified herein, the alkyl group includes a primary alkyl group, a secondary alkyl group, and a tertiary alkyl group. From the burning of smoke: two = sub-: obtained divalent atomic group, and can be derived from the general formula unless otherwise specified herein, otherwise the perfluoroalkane is one atom or all hydrogen atoms replaced by fluorine Any of the hydrogen atoms or all of the hydrogen atoms of the genus β 虱 经 氟 氟 ; ; ; = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = ^ 201144264 38471pif carbyl, diradical, cyano, nitano, (iv), thiol, thiol, alkoxy, corpse 2, 2, 1, (4), §, base, silk, secret a base, a ketone group, a soil, a king fluorocarbonate, a cycloalkyl group, a heterocycloalkyl group, a propyl group, a benzyl group, an aryl group, a heteroaryl group, a derivative thereof, and a combination thereof. Unless otherwise specifically stated herein One to three are replaced by N, 〇, s, and p. Otherwise, the word "hetero" means the miscellaneous matter selected from the group consisting of carbon atoms. Unless otherwise specified in this article, the non-function base means a carbon atom. a straight or branched chain filament; a burnt dibasic meaning has a dih radical of i to ι〇 = atom; a fluorenyl group means a dilute 2 having 2 to 1 () carbon atoms; a dilute propyl means having 2 Allyl groups to 1 () carbon atoms; alkoxy groups = silk groups having from i to Π) carbon atoms; perfluoroalkyl groups means all-wei groups having from i to 10 carbon atoms; And means a fluorenyloxy group having from 1 to 3 carbon atoms; a cycloalkyl group means a cyclic fluorenyl group having from 3 to 32 carbon atoms; Heterocycloalkyl means a heterocycloalkyl group having 2 to 32 carbon atoms; aryl = an aryl group having 6 to 30 carbon atoms; and a heteroaryl group having a heteroaryl group of two broad carbon atoms. H(10) As used herein, Me is an abbreviation for sulfhydryl. The photoacid generator of one embodiment of the present invention is represented by the following formula [Equation 1]

0 ?1 h2 h2

A+-0—S—C_C —C —O

II IO 〇 2 201144264 38471pif In the above formula 1, (^ and Q2 each independently represent a halogen atom, and preferably a fluorine atom. η is an integer of 0 to 5, and preferably an integer of 〇 to 2. X represents Any one selected from the group consisting of an alkyldiyl group, a dilute diyl group, NR1, s, anthracene, CO, and a combination thereof, and R represents a group consisting of a hydrogen atom and an alkyl group Any one selected. X may represent any one selected from the group consisting of: -〇-, -〇CH2-, -OCH(Cl)-, -CO-, -coch2-, -COCH2CH2 -, -CHr, -CH2CH2-, -CH2-〇-, -CH2-〇-CH2-, -CH2CH2-0-, -CH2-0-CH2CH2-'-CH2CH2-0-CH2- > -CH2CH2CH2-0 - ' -ch2-o-ch2ch2ch2-, -CH2CH2-〇-CH2CH2-, -ch2ch2ch2-0-ch2- ^ -CH(CH3)- ^ -C(CH3)2CH2- ^ -CH(CH3)CH2- ' - CH(CH2CH3)- . -CH(OCH3)- ' -C(CF3)(OCH3)- ' -CH2-S- ' -CH2-S-CH2- ' -CH2CH2-S- ' -CH2-S-CH2CH2- '-CH2CH2-S-CH2- '-CH2CH2CH2-S- '-CH2-S-CH2CH2CH2-, -CH2CH2-S-CH2CH2-, -CH2CH2CH2-S-CH2- '-CH(CH2)CH- '-C( CH2CH2)- '-CH2C0-, -CH2CH2CO-, -CH(CH3)CH2CO-, -CH(OH)-, -C(OH)(CH3)-, -CH(F)-, -CH(Br)-, -CH(Br)CH(Br)-, -CH=CH- > -CH2CH=CH-^ -CH =CHCH2- ^ -CH=CH-0- > -CHNCH-S-, and -CH=CHCO-. In the above formula 1, Y represents a cycloalkyl group having 3 to 30 carbon atoms and has 3 to Any one selected from the group consisting of cycloalkenyl groups of 30 carbon atoms 0 201144264 3847 lpif Y may represent any one of the groups consisting of the following groups: adamantyl group, norbornyl group a polycyclic cycloalkyl group having a norbornyl group having 1 to 30 carbon atoms, a mono-cycloalkyl group having 3 to 14 carbon atoms, a bicyclic cycloalkyl group having 4 to 20 carbon atoms, having a tricyclic cycloalkyl group of 10 to 30 carbon atoms, and a tetracyclic cycloalkyl group having 1 to 3 carbon atoms. In the hydrogen atom of Y, one to five hydrogen atoms may be substituted by any one selected from the group consisting of: a group having from 丨 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms a perfluoroalkyl group having up to 4 carbon atoms, a perfluoroalkoxy group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, a cyano group, a nitro group , amine, thio, thiol, decyloxy, c〇R, and c〇〇R,. R' represents any one selected from the group consisting of an alkyl group and an aryl group. Preferably, 'Y' may be any one selected from the group consisting of the following formulae 1-a to i_i. 12 201144264 [Formula l-a] [Formula 1-b]^T^Rl1)b [Formula 1-c] [Formula 1-d]

[Equation 1-e]

[Equation 1-h]

[Formula 1-i] 13 201144264 38471pif In the formulae 1-a to 1-i, 'Rn and Ri2 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a perfluoroalkyl group, a perfluoroalkoxy group, a halogen. Atom, a sulfhydryl group, a thiol group, a cyano group, a nitro group, an amine group, a thio group, a thiol group, a decyloxy group, OR1, COR', and COOR'. R· represents any one selected from the group consisting of an alkyl group and an aryl group. In the above-mentioned subscripts, 'a, c and d each independently represent an integer from 〇 to 9; b represents an integer from 0 to 11; e represents an integer from 〇 to 15; and f represents an integer from 0 to 7; 0$ c+d $ 17 'At the same time 〇 $ c+f $ 15. Preferably, 'in the formulae 1-a, l~b, l_d, and Ι-g, r" may represent any one selected from the group consisting of: a hydrogen atom having 1 to 6 carbon atoms An alkyl group, an alkoxy group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, a perfluoroalkoxy group having 1 to 4 carbon atoms, having 1 to 6 carbon atoms A hydroxyalkyl group, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amine group, a thio group, a methylthio group, and a methoxy group. Further, in c, Ι-e, Ι-f, 卜h and 1-1, Ru and Rl2 each independently represent any one selected from the group consisting of: hydrogen atom, having 1 An alkyl group of up to 6 carbon atoms, an alkoxy group having from 丨 to 6 carbon atoms, having! Perfluorononyl group to 4 carbon atoms, perfluoroalkoxy group having 1 to 4 carbon atoms, hydroxyalkyl group having 1 to 6 carbon atoms, halogen atom, trans group, cyano group, nitro group, amine Base, thio, methylthio, methoxy, and combinations thereof. Preferably, the moiety represented by the following formula 3 may represent any one selected from the group consisting of the following formulas i-i to j-xx, and the formula 3 is a compound represented by the formula 1 shown above. The anion part. -x-201144264 [Equation 3] ? 1 h2 h2 -0-s-c-C -G -o- Jl i 〇 〇2 [Form l-i to l-xx] -o

o f2 h2 .s-c, A c h2 o 〇 h2 O F2 H2 〇-S-CvAn -〇 w CO 0 h2 [1-i] 0 f2 h2crVSA 0 h2 11-tv ] 1-ii]

o f2 h2 VC c -〇Λ v '〇 h2

[1-vi ] 9 f2 h2 〇 h2 [1-vii ]

[1-viii] 0 F2 H2 〇4rVc'〇 0 H2 [1-x]

-0 〇 f2, r - S-c, ^ L 〇 H2 O F2 H2 person 〇 co o h2 [1-xii]

<y〇H h2 r^\^os 〇 〇 o H2 -o o f2 h2 I, έ -〇, 〆〇 \, C 〇 ο Η2 ον

[1-x [1-xiv] 15 201144264 38471pif O F2 H2

[1-xviii ] o f2 h2 o-s-c ϋ , , c 0一 o h2 [1-xvii ]

o f2 h2 〇Js-c c 〇 h2 [1-xvi]

O F2 h2 crVC, A 〇 [1-xx ] [1-xix ]

When a light source such as ArF is used, the above photoacid generator obtained by introducing an alicyclic ring into the compound represented by the above formula 3 can provide an ability to adjust the acid diffusion rate and exhibit such as high permeability. A photoacid generator characterized by the anion portion of the compound represented by Formula 1. In Formula 1, A+ represents an organic relative ion. Specifically, the portion represented by the following formula 2 may represent any one selected from the group consisting of the following formulas 2a and 2b, and the formula 2 is a cationic portion of the compound represented by Formula 1. 16 201144264 [Formula 2] A+ [Formula 2a]

[Formula 2b]

R3 上上式幺a is ou i Its 111 private photo 2, 夂 2b ' Ri and R2 each independently represent the selected group of the following groups: hydrogen atom, silk, women's two A fluoroalkyl group, an aryl group, and a combination thereof, J· Ri and & can be bonded to each other. To form a saturated or unsaturated hydrocarbon ring having 3 to 3 carbon atoms. R4 means that any one of the group consisting of a bribe _ constituting a group of atoms, an alkyl group, an alkoxy group, an aryl group, a furnace, an alkoxy group, an alkoxycarbonylmethyl group, a sulfur Phenoxy groups, and combinations thereof. The ruler 3 and the ruler 5 each independently represent any one selected by y ό #·························· Earth-based 'In Formulas 2a and 2b, examples of the alkyl group include ρ, ethyl, propyl, 17 201144264 38471pif isopropyl, n-butyl, pentyl, including methoxy, ethoxy, Octyloxy. a hexyl group, and an octyl group, and a propoxy group of alkoxy group, a butoxy group, a hexyloxy group, and, in addition, a group consisting of the formula _ 2-χχ of the formula 2 can be represented by the following formulas 2-i to the cationic part of the compound shown, any one, the formula 2 is of the formula! Table [Formula 2-i to j

18 201144264

F [2-ix ]

[2-xi ] [2-xii ]

Or

[2-xiii] [2-Χ]

CH H3C-S + 00

-S

[2-xvi ] [2-xv]

[2-xvii ] [2-xviii] [2-xix ] [2-xx] The portion represented by Formula 2 may represent any one selected from the group consisting of the following Formulas 3a and 3b, and the Formula 2 is The cationic portion of the compound represented by Formula 1. 19 201144264 38471pif [Formula 3a] i +

[Formula 3b] I +

In Formulae 3a and 3b, R! represents any one of the following: hydrogen atom, alkyl group, fluorenyl group, hologram group, and combinations thereof.丞 and R3 each independently represent a selected one of the following groups: a hydrogen atom, a pyridyl group, a fluorenyl group, a full-length group, and combinations thereof. R4 represents any one selected from the group consisting of a aryl group, a decyl group, a aryl group, an aryl group, a sulfur alkoxy group, a benzyloxycarbonyl thiophenoxy group, and combinations thereof. . In the formulae 3a and 3b, examples of the alkyl group include mercapto group, ethyl 'propyl isopropyl group, n-butyl group, strepyl group, hexyl group, and octyl group, and the oxy group and the oxime group include an anthracene group and an ethoxy group. A group, a propoxy group, a butoxy group, a hexyloxy group, and a 2 octyloxy group. _ 201144264 Further, the portion indicated by the formula 2 may be any one selected from the group consisting of the following formulae 3-i to 3 to ix, and the formula 2 is a cationic portion of the compound represented by the formula 1. [Formula 3-i to 3-ix]

A method of producing a photoacid generator represented by Formula 1 of another embodiment of the present invention includes a first step of dissolving a compound represented by the following Formula 8 in a solvent, and reacting the solution with a reducing agent to obtain a formula 6 a compound represented by the second step: reacting a compound represented by the following formula 7 with a compound represented by the following formula 6 in the presence of a basic catalyst to obtain a compound represented by the following formula 4; and a third step: The compound represented by Formula 4 is subjected to a substitution reaction with a compound represented by the following formula, and thereby a compound represented by Formula 1 is obtained. The first step includes a process of dissolving a compound represented by the following formula 8 in a solvent, adding a reducing agent, and thereby obtaining a compound represented by the following formula 6. 201144264 38471pif

U M+ -0-S-c1-r2 ^ η Y c^ 〇q2 0, R6 [Formula 6] M+ In Formula 6 and Formula 8, in the group consisting of column groups, 6 represents an alkyl group and can be specified The ground is represented by any of the following: a methyl group, a tribromomethyl group, and a QaQ2, each of which is methyl, ethyl, propyl, and butyl. It means that the wire (4) (four) is composed of the lower_cut. Yue and κ+. Any one selected from the group: Li+, Na+ is used to dissolve the agent in the step reaction, and any solvent can be used as long as the solvent can dissolve the vinegar reaction represented by the formula 8. And causing any one of the group I, the agent 2, and the substance 1 to be selected: the latter, the oxime, the ether, the lactone, the guanamine, preferably, the alcohol-based solvent can be combined with the following And any one of them is used: dichlorobenzene, chlorine/structure == selected from the group consisting of toluene, tetrahydrogen, di-W-amine, ethyl chloride, acetonitrile, but the invention is not intended to be limited to such solvents . Stone 'and combinations thereof, the alcohol-based solvent may be any one selected from the group t of the following alcohols. 201144264 3847lpif · sterol, ethanol, propanol, isopropanol, n-butanol, butanol, side oxygen Butanol, deca-ol, hydrazinol, heptanol, dipentyl alcohol, allyl alcohol, ethoxylated methanol, methoxyethanol, ter-2-propanol, benzyl alcohol, phenylethyl alcohol, ring Hexanol, soil y containing earthen clothes, decyl alcohol, tetrahydrofurfuryl alcohol, tetrahydrool, cyanobutanol, 4,yl-2-butanone, and combinations thereof, the invention is not intended to be limited to such solvents . One + may be selected from the group consisting of NaBH4, LiAlH4, BHa-THF, NaBH4-AlCl3, NaBH4-LiCl, LiAl(〇Me)3, and combinations thereof. The compound represented by Formula 8 and the reducing agent may be used in a molar ratio of 1:1 to 1:5 using a molar ratio of 'and a preferred illusion: 2 to 1:3.5. When the compound represented by Formula 8 and the reducing agent are used in the above molar ratio, the product yield with respect to the amount of the reducing agent to be used may be increased. Specifically, the first reaction may include the steps of dissolving the compound represented by Formula 8 in the above-mentioned solvent in an ice bath, adding a reducing agent to the solution dropwise to prepare a reaction mixture liquid, and flowing the reaction mixture liquid from Remove the ice from the ice and heat and disturb the liquid of the reaction mixture. The stirring process is preferably carried out at 20 ° C to 120 ° C for 2 to 6 hours, and more preferably at 6 (TC to 100 ° C for 3 to 5 hours. When the stirring process is carried out in the above temperature and time range The yield of the product can be increased, and the formation of by-products can be minimized. The reaction of the liquid of the reaction mixture is terminated by quenching to remove the solvent, and then the reaction product is collected. Regarding the method of collecting the reaction product, any can The reaction mixture solution 23 201144264 may be used by a conventional method of removing a solvent and collecting the reaction product, and for example, a recrystallization method may be used, by using a solvent which readily dissolves the obtained compound, and a compound which is aged and disintegrated. A method of curing a mixture of solvents to cure an anti-deer product, a method of extracting a reaction product concentrate with a solvent, or a method of enriching a reaction product. A preferred example of a method of collecting a reaction product that can be used is the following method: a liquid from a reaction mixture The solvent is removed, the residue is dissolved in distilled water, then the solution is acidified to a pH of 5 to 6, and the liquid of the reaction mixture is concentrated and again in the concentrate. The alcohol is added to remove the inorganic salt in the form of a slurry, the residue is filtered, and the filtrate is crystallized using diethyl ether or the like. The compound represented by the formula 8 can be produced by the following steps: an intermediate preparation step: alkoxide and halogenation Reacting to form a dialkoxy group having two alkoxy groups, followed by oxidizing two alkoxy groups of the dialkoxy halide to form a compound represented by the following formula 9; and a continuation step: The compound represented by 9 reacts with an inorganic sulfite to form a compound represented by Formula 8. [Formula 9] Q3~c1-c2-?-〇__r q2 6 In Formula 9, & represents an alkyl group, and Any one selected from the group consisting of: methyl, trimethyl, trigas; ', methyl, dimomethyl, ethyl, propyl, and butyl; and to Q3 Each of them is independently a self-priming atom, and preferably a fluorine atom. 24 201144264 38471pif, a sinter oxide: can be an alkyl halide 'and can be specifically perfluorodecane, dibromodifluorodecane, Permethyl bromide or perchloromethane. _ Γ Γ, in the preparation step 'make the oxide and halide in the alcohol group , in the reaction, and the compound can also be reacted with sulfite oil (Na2 bis = (NaHC03). In addition, the reaction of the second oxy group of the oxy-chemical compound can be obtained by the above-mentioned reaction. A specific example of an oxidizing agent that can be used in the presence of an oxidizing agent is a certified person. 5. In particular, sodium hydrogen sulfite can be used as the inorganic sulfite in the contacting step and the reaction can also be added. After the sodium chloride carbonate (NaHC03) is carried out, when the reductive reaction is carried out using the sub-hydrogen (IV), the compound represented by the formula 8 can be produced by oxidizing the organic sulfonate thus formed. In this case, it can be used. Hydrogen peroxide (Ah), sodium tungstate (NaWO4) or the like is used as the oxidizing agent. The second step includes a process in which a compound represented by the following formula 7 is reacted with a compound represented by the formula 6 in the presence of a basic catalyst, and thereby a compound represented by the following formula 4 is obtained. Further at 25 201144264 •/V/ · · [Equation 7] α5-4χ4ί^0 [Formula 4] M+-. - In Equation 7, 'Ql, Q2, and A each independently represent a dentate:: to = gas atom; and η represents. An integer of up to 5, and preferably any of the quaternary ridges and γ have the same meaning as described above for the compound represented by Formula 1, and the definition will not be repeated. Newumΐί is used as an experimental catalyst by any of the publications of the magazine: triethylamine, diethylamine, _, and diethyl = fine. When the alkaline stimulating agent is used for reflection in the second step, the desired product can be obtained in the reaction, and therefore, the reaction of the second step which can increase the reaction can be carried out in the presence of a solvent, and the composition of the substance The ethnic group t is selected as the solvent: brewing, testing, sputum: each: alcohol, and combinations thereof. Preferably, the solvent may be selected from the group consisting of the lower jaws, the dichloromethyl form, the chloroform, the 26 201144264 38471pif ethyl acetate, and the group of dichloroethane, acetonitrile, hydrazine. In the reaction, the compound represented by Formula 6 and the compound represented by Formula 7 may be used in a molar ratio of 1:1 to 1:3, and preferably i, :u ^ 1丄5 Moer than used. When the compound represented by Formula 6 is reacted with the compound represented by Formula 7 in the above molar ratio, the two compounds can be 'completely consumed, and thereby the reaction efficiency can be increased. Further, the compound represented by Formula 6 in the reaction may be used in a molar ratio of 1:1 to 1:4, and preferably used in a molar ratio of 1:1 1 to 1.2. When the compound of the formula 6 is used in a reaction with a basic catalyst in the above molar ratio, the reaction time can be accelerated and the removal of any residual basic catalyst can be made easier. The second step reaction may specifically include a process of dissolving a compound represented by Formula 6 and a basic catalyst in a solvent, and stirring the mixture at an elevated temperature to add a compound represented by Formula 7 dissolved in a solvent to In the compound, and then the resulting mixture was stirred. The stirring process is preferably carried out at a temperature of from 40 ° C to 120 ° C for 5 to 6 hours' and more preferably at 6 Torr. (: to 9 (2 to 3 hours at TC temperature.) When the stirring process is carried out in the above temperature and time range, the product yield can be increased, and by-product formation can be minimized. Quenching is terminated to remove the solvent, and the reaction product is crystallized after the passage of P. Thus, the compound represented by Formula 4 can be obtained. Regarding the crystallization method, as long as the method removes the solvent from the liquid of the reaction mixture and crystallizes the reaction product. A common method, any method can use 27 201144264 WI f ▲ free / storm & without limitation. However, preferably, the reaction mixture can be washed, then the organic layer is separated to remove the solvent, using the column layer The residue is separated, and then the reaction product is dried in a vacuum to obtain a reaction product. The second step includes a process of subjecting a compound represented by Formula 4 shown above to a compound represented by the following Formula 5, and Thus, a compound represented by the following formula 1 is obtained. "4 R] A + Z - In the formula 5, Z- represents any one selected from the group consisting of the following ions: (〇S02CF3>, (〇 S〇2c4F9)·, (os〇2c8Fi7)_, (N(CF3)2)- '(N(C2F5)2)- . (N(C4F9)2) > (C(CF3)3). > (C(C2F5)3)-, (C(C4F9)3)-, F-, ci-, Br-, I_, BF4_, AsF6_, and PF0-; A+ represents an organic relative ion. Due to the specific definition of this organic relative ion It is the same as the definition given to the compound represented by Formula 1, and therefore will not be repeatedly described. The compound represented by Formula 4 and the compound represented by Formula 5 may be used in a molar ratio of 1:1 to 5:1. The m:i to 3:1 molar ratio is used, and even more preferably at a molar ratio of 1:1 to 2: 1. When the compound is used in the above molar ratio, the reaction treatment time can be minimized, and Any side reaction caused by the use of an excessive amount of the reaction product can be suppressed. The substitution reaction can be carried out by using a recrystallization method, or a solvent (good solvent) which satisfactorily dissolves the salt can be used and poorly dissolved 28 201144264 38471pif a method in which a mixture of a salt solvent (poor solvent) is used to cure and recover a salt obtained from the reaction, and a method of extracting with a solvent, or concentrating and recovering the obtained salt Preferably, the compound is dissolved in dioxane and water to form two layers, which can then be stirred to effect a substitution reaction. In the case of using such a two-layer reaction, it is advantageous in that No other method is required to separate the product. Stirring can be carried out for 2 to 6 hours, and can also be carried out for 2 to 4 hours. When the reaction is carried out in the above time range, the product yield can be maximized. In the case of the compound represented by Formula 1, the compound represented by Formula 1 can be produced by an efficient and simple method. The photoresist composition according to another embodiment of the present invention contains the photoacid generator represented by the above formula 1. The photoresist composition is based on the composition of a conventional photoresist composition, and thus the description about the photoresist composition will not be repeated herein. The photoacid generator of the present invention can generate an acid upon exposure, the acid having a low diffusivity, a short diffusion distance, and exhibiting an appropriate acidity so that the line width roughness (LWR) characteristics can be improved, and it is used in a process. The dissolution in a solvent such as pure water can be controlled. Further, the method of producing the photoacid generator of the present invention can produce the above photoacid generator via an efficient and simple method. [Embodiment] Hereinafter, the present invention will be described in detail by way of examples, so that the present invention can be easily carried out by those having ordinary skill in the art. However, the invention can be carried out with various modifications and modifications, and the scope of the invention is not limited to the examples described herein. Synthetic photoacid generator [Synthesis example 1 of photoacid generator] Synthesis of adamantyl-3,3-difluoro-3-reverse-propyl ether diphenylmethylphenyl salt (Adamantyl-3,3- Difluoro-3-sulfo-propyl ether diphenyl methylphenyl sulfonium salt) (Step 1) As shown in the following Reaction Scheme 1, 83 g (0·376 mol) 1,1-difluoro-3-methyl in an ice bath Sodium oxy-3-oxopropane monosulfonate was dissolved in 160 ml of methanol (Me〇H) as a solvent and 12 liters of tetrahydrofuran (THF). 44 g (1.16 mol) sodium hydride (NaBH4) was slowly added dropwise to the solution to prepare a reaction mixture liquid. After the dropwise addition was completed, the reaction mixture liquid was removed from the ice bath and heated to 60X:. While maintaining the temperature, the reaction mixture liquid was stirred for about 4 hours. The reaction mixture liquid was quenched with distilled water, and then the solvent was removed. The crude reaction mixture was dissolved in distilled water, and the solution was acidified to 5 to 6 with concentrated hydrochloric acid. The acidified reaction mixture was concentrated, and methanol was again added thereto. The slurry thus obtained was filtered to remove inorganic salts. The filtrate obtained by removing the slurry was washed twice with hexane, and the sterol layer was again concentrated, followed by crystallization using diethyl ether. 201144264 A white solid obtained by crystallization was dried in vacuo, and the structure of the compound was determined by 1H-NMR. Thus, 5 g (0.346 mol, yield 95%) of 1,1-di U-pyridyl-1-pyristyl sodium was obtained. ^-NMR (D20): (ppm) 2.38 (t, 2H), 4.18 (t, 2H) [Reaction Scheme 1]

+ MeOH

NaBH4 THF, MeOH Ο

NaO^C^y〇Me With respect to the reference '1,1-difluoro-3-indolyl-3-oxopropane-1-sulfonic acid shown above can be produced by a reaction such as the following Reaction Scheme 2 sodium. [Reaction Scheme 2] in OMe + CF2Br2

OMe KHS05

ΟΜθ

Ν32§2〇4 NaHC03 80C

N32S2〇4 NaHC03 MeOH

H2〇2 r Na2W〇4

Na03S

OMe (Step 2) As shown in the following Reaction Scheme 3, 20 g (0.101 mol) of 1,1-difluoro-3-pyrimidin-1-ylic acid and 23 ml (step) produced in the step i are obtained. 0.165 mol of triethylamine (EtsN) was dissolved in 400 ml of ethyl acetate, and the thus obtained solution was stirred at 80 °C. 5小时。 The reaction mixture was heated and stirred for 2.5 hours. The reaction mixture was stirred and stirred. After completion of the reaction of the reaction mixture, the reaction mixture was washed three times with 200 ml of a 1N hydrochloric acid solution, and the reaction mixture was washed once with 200 ml of a 10% sodium carbonate solution. The organic layer of the reaction mixture was separated' and the solvent was removed. The reaction product was separated by column chromatography using tannin and the reaction product was dried in vacuo. The dried reaction product was subjected to 1H-NMR' and the structure was determined. Thus, 30 g (yield 80%) of 3-(adamant-1-yloxy)-1,1-difluoropropanzein-1_glycide represented by the formula A in the following Reaction Scheme 3 was obtained. (3-(adamantan-l-yloxy)-l,l-difluoropropane- 1-sulfonic acid salt) 〇h-NMR (dioxin-indole, tetradecyl decane): (ppm) 1.67-1.98 (m) , 15H), 2.45 (t, 2H), 4.52 (t, 2H) [Reaction Scheme 3]

— L 〜0H ◦ f2 (Step 3) As shown in the following Reaction Scheme 4, the 8.5 gram (0. 0255 mol) 3-(adamantan-1-yloxy)-1 was produced in the step 2. , difluoropropane-1-sulfonate and 10 g (〇·0234 mol) of triphenylsulfonylbenzene triphenylsulfonyl sulfonate salt represented by formula B in the following Reaction Scheme 4 32 201144264 A reaction mixture having two layers was formed in 100 liters of methylene chloride (MC) and 1 liter of water. The reaction mixture was stirred vigorously for 3 hours to allow the reaction (two-layer reaction) to proceed. When the mixing of the reaction mixture was completed, an aliquot of the organic layer was taken to examine the progress of the reaction by 19F-NMR. When the reaction is complete, the organic layer is collected and the solvent is removed. The thus obtained slurry was washed using dioxane as a good solvent and hexane as a poor solvent, and thereby a solid was obtained. The solid is dried under reduced pressure' and thereby the compound represented by the formula B in the following Reaction Scheme 4 is obtained. Thus, 13.3 g (yield 94.3%) of the adamantyl_3,3-difluoro_3_reverse-propyl ether diphenyl fluorenyl group represented by the formula C in Reaction Scheme 4 was obtained. Phenyl sulfonium salt' and the structure was determined by ih_NMr. h-NNIR (gas imitation - ί/3 ' 四曱基石夕烧): (ppm) 1 98 (m 15H), 2.45 (t, 2H), 2.47 (s, 3H), 4.76 (t, 2H), 7.48 (d,2H)' 7.65-7.76(m, 12H) ' ' [Reaction Scheme 4]

33 201144264 38471pif Synthetic Resin [Synthesis Example 1 of Resin] Add 3 double rings [2· 2. 1] G-5-Wo-2 in a molar ratio of 1:1:1 (33 parts: 33 parts: 33 parts) - Benzyl-3-propionic acid tert-butyl vinegar, propyl methacrylate (2-methyl-2-adamantyl acrylate) and γ-butyrolactone methyl acrylate (2-o-acrylic acid acrylate) Tetrahydrofuran_3_yl ester), and 1,4 -dioxane which is equivalent to 3 times the total mass of the reaction monomers is used as a polymerization solvent. Azobisisobutyronitrile in a ratio of 4 mol% based on the total molar amount of the monomer was used as the initiator' and the system was at 65. (The reaction was carried out for 16 hours. After the reaction, the reaction solution was immersed in a solution, and the sediment was dried in a vacuum. Thus, a resin represented by the following formula 10 was obtained. The copolymer obtained as a precipitate had 8, Weight average molecular weight of 500. [Formula 10]

Preparation of Photoresist [Comparative Example 1] 100 parts by weight of the resin represented by Formula 10 obtained in Synthesis Example 1 of the resin, and 4 parts by weight of triphenyl nickel trifluorosulfonate were used as the photoacid generator (PAG), And 0.5 parts by weight of tetramethylammonium hydroxide as a basic additive 34 201144264 (BASE) dissolved in hydrazine, _ parts by weight of propylene glycol, and then the solution was transitioned through a 〇' 2 micron membrane transition. & This prepares a photoresist solution. The photoresist solution was applied to the substrate using a spinner, and the photoresist solution was dried under 11 Torr for 90 seconds to form a film having a thickness of 20 μm. The film thus formed was exposed using an ArF excimer laser stepper (number of lens apertures: 〇.78), and heat treated at 110 for 90 seconds. The thus formed film was visualized using a 3.8 wt% aqueous solution of tetrahydric ammonium hydroxide for 4 seconds, followed by silking and drying the film. Thereby, a photoresist pattern is formed. ^ [Example 1] A photoresist solution was prepared in the same manner as in Comparative Example 1, except that 3 parts by weight of adamantyl-3 which was produced in Synthesis Example 1 and represented by Formula C in Reaction Scheme 4 was used. 3-Difluoro-3-sulfo-propyl ether dipyridylmethyl-based salt as a photoacid generator. Evaluate the properties of the photoresist solution. [Example 2] A photoresist solution was prepared in the same manner as in Comparative Example 1, except that 5 parts by weight of the adamantyl group 3, 3 which was produced in Synthesis Example 1 and represented by the formula C in Reaction Scheme 4 was used. - Difluoro-3-nextyl-propanoid dipyridyl phenyl phenyl salt as a photoacid generator. Evaluate the properties of the photoresist solution. [Example 3] A photoresist solution was prepared in the same manner as in Comparative Example 1, except that 7 parts by weight of adamantyl-3 which was produced in Synthesis Example 1 and represented by Formula C in Reaction Scheme 4 was used. 3-Difluoro-3-sulfo-propyl ether diphenylmercaptophenyl sulfonium salt as a photoacid generator. Evaluate the properties of the photoresist solution. The properties of Comparative Example 1 and Examples 1 to 3 were evaluated, such as sensitivity, 35 201144264 38471 pif resolution, and LWR, and the results are presented in Table 1 below. In the case of LWR, the pattern roughness of a 10 μm line-and-space (L/S) pattern formed after development was observed, and the degree of improvement of LWR was divided into numbers of 1 to 5. Grade, and the pattern level obtained in Comparative Example 1 is 丨. A larger number indicates a better LWR feature. In the case of sensitivity, the exposure amount of 〇. 1〇 micron line width/interval (L/S) pattern is specified as the optimum exposure amount, and the sensitivity is set equal to the optimum. At the time of exposure, the minimum pattern size obtained by imaging is specified as the resolution. [Table 1] Resin (100 parts by weight) PAG (1) (parts by weight) base (2) (parts by weight) Sensitivity (min/joule resolution (nano) LWR Example 1 Synthesis of resin 1 3 0.5 17 70 4 Example 2 Synthesis of Resin Example 1 5 0.5 16 80 3 Example 3 Synthesis of Resin Example 1 7 0.5 13 70 3 Comparative Example 1 Synthesis of Resin Example 1 3 0.5 15 90 2 (1) Photoacid Generator (PAG) Examples 1 to 3: adamantyl_3,3-difluoro_3_sulfo-propyl ether diphenylmercaptophenyl sulfonium salt 36 which was produced in Synthesis Example 1 and represented by the formula C in Reaction Scheme 4. 201144264 38471pif Comparative Example 1: Triphenylsulfonium triflate (2) Ingredient additive (BASE): tetramethylammonium hydroxide is introduced into the anion of the photoacid generator by introducing an alicyclic ring The photoacid generator (pAG) used in Examples 1 to 3 was formed. The acidity was similar to that of the existing triflate or nonaflate photoacid generator. The photoacid generator of the acidity of the trifluoromethane acid salt has a low acid diffusivity and a short diffusion distance. Therefore, the light The generator has characteristics suitable for achieving a finer L/S pattern. When studying the results of the analysis of the properties of Table 1, the photoacid generator is in LWR and compared to the existing triflate type photoacid generator. The superior performance is demonstrated in terms of resolution. When irradiated with light, the anion towel which introduces the aromatic ring into the photoacid generator exhibits excellent results even in terms of transparency. Once the ship line is generated from the photoacid, the accompaniment form axis, Then, the aromatic ring does not affect the turning degree at all, and depending on the aromatic ring, it is possible to control the diffusion rate of the acid and the diffusion distance, which is not different from the characteristics of the existing photoacid generator. Although this (4) [卩 is better implemented _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Specialized by the definition of the area. Supporting farmers [simple description of the schema] benefits. Chuan, [main symbol description] M. 〇37

Claims (1)

201144264 3847 lpif VII. Patent application scope: L A photoacid generator represented by the following formula 1: In the formula i, any of Qi and Q2 selected from the group consisting of a ring of 30 carbons to 3G carbon atoms and a % of a weak base having 3 to solid ash atoms independently represent a halogen atom; X ^ shows = selected from the group consisting of the following groups: NR, s, 〇, c 〇 and combinations thereof, wherein R, J is a group of 虱 atoms and alkyl groups. η represents an integer from 0 to 5; and, Α+ represents an organic relative ion. The photoacid generator according to claim 1, wherein the selected one of the groups consisting of γ ί 列 基 产 r r 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 It includes 2 counties of the norbornene group, a single looped loop filament having 3 to 14 carbon atoms, having 4 base ' and having 3 to. The four rings of two carbon atoms = two ones. The photoacids described in item i of the patent application range are not selected from the group consisting of the following formulas: a phantom-i 38 201144264 38471pif [Formula 1-a] 1-b] [Formula 1-c] [Equation 1-e] [Equation 1-h] 39 201144264 38471pif wherein in the formulae 1-a to li, 1^ and R1Z may each be independently substituted by any one selected from the group consisting of alkyl, alkoxy, perfluoroalkyl , perfluoroalkoxy, dentate atom, hydroxyl, carboxyl, cyano, nitro, amine, thio, thiol, methoxy, OR', COR, and COOR, wherein R, represents Any one selected from the group consisting of a base and an aryl group; a, c, and d each independently represent an integer from 〇 to 9; b represents an integer from 〇 to 11; e represents an integer from 0 to 15; and f represents 〇 to An integer of 7; and 0 £ c+d $17, and 0 $c+f $15 ° 4. The photoacid generator according to claim 1, wherein X in the formula 1 represents the following Any one of the groups formed by the group: _〇_, _〇CH2-, -OCH(Cl)-, -CO-, -COCH2-, -COCH2CH2-, -CHr, -CH2CH2-, -ch2 -o-, -ch2-o-ch2-, CH2CHrO-, -CH2-0-CH2CH2-, -CH2CHrO-CH2-, -ch2ch2ch2-o-, -ch2-o-ch2ch2ch2-, -CH2CH2-0-CH2CH2- , -CH2CH2CH2-0-CH2-, -CH(CH3)-, -C(CH3)2CH2-, -CH(CH3)CH2 -, -CH(CH2CH3)-, -CH(OCH3)_, _C(CF3)(OCH3)_, _CHrS_, _CHrS-CH2-, -ch2ch2-s-, -ch2-s-ch2ch2-, -ch2ch2-s -ch2-, -CH2CH2CH2-S-, -CH2-S-CH2CH2CH2-, -CH2CH2-S-CH2CH2-, -CH2CH2CH2-S-CH2-, -CH(CH2)CH-, -C(CH2CH2)-,- CH2CO-, -CH2CH2CO-, -CH(CH3)CH2CO-, -CH(OH)-, -C(OH)(CH3)-, -CH(F)-, 201144264 3»47ipit -CH(Br)-, -CH(Br)CH(Br)-, -CH=CH-, -CH2CH=CH_, -ch=chch2-, -ch=ch-〇-, -CH=CH-S-, and -CH=CHCO-. b. The selected one of the ethnic groups—the second one: the anion portion of the composition of the formula 1-i to 丨_xx: a formula 3 is the compound represented by the formula [Equation 3] 0 9ι [Formula 1-i to l-xx] [1-ii] [1-iii] [1-iv] t 1'V] U-x] f 1'Xi ] [1-ix] f 1-xii ] 41 201144264 V, f2 h2 '°-rcvc 0 s2 ° xy°ro H2 [1-xiii ] -〇\%^-Cn〇H 9. H2 -〇1, cA&lt; 〇h2 [1- Xvi] 9\ H -〇-Vc~c [1-xiv ] 0 f2 h2 [1-xvii ] 0 F2 H2 [1-xv] 9; f2 h2 0 h2 0 [1-J&lt;ix 】 OH [1-XX] 6. A method of producing a fine by the following formula *, the method comprising: the first step: dissolving the compound represented by the following formula 8 in a solvent, and subjecting the solution to reduction The reaction of the agent to obtain a compound represented by the following formula 6; the second step: reacting the compound represented by the following formula 7 with the compound represented by the following formula 6 in the presence of a basic catalyst, and thereby obtaining 4: 4 And a third step of subjecting the compound represented by the following formula 4 to a substitution reaction with a compound represented by the following formula 5, and thereby obtaining a gas compound represented by the following formula: 42 201144264 JO*+/ ιριι [Equation 8] S—C—C —co—R6 II I 0 O 〇2 M+ [Equation 6] 9 ?1 H2 h2 M+ -0—S—C—C —C —OH II IO 〇2 [Equation 7] Q^x^ -0 [Formula 4] II I 〇 〇 2 [Formula 5] A+Z- [Formula 1] 0 ?1 h2 h2 A+.〇_s_e-c -c -o O 〇2 wherein in the formula 1, the formula 4, the formula 5, the formula 6, the formula 7, and the formula 8, Κ·6 represents a burnt group; Qi And Q2 and Q5 each independently represent a halogen atom; Y represents any one selected from the group consisting of a cycloalkyl group having 3 to 30 carbon atoms and a cycloalkenyl group having 3 to 30 carbon atoms; 43 201144264 X represents any one selected from the group consisting of: an alkyl group: an enediyl group, NR', S, an anthracene, a C〇, and a combination thereof, wherein R represents a group consisting of a hydrogen atom and a burnt group. Any of the selected ones η represents an integer from 0 to 5; Α+ represents an organic relative ion; Μ+ represents any one of the groups consisting of the following ions: Li+, Na+, and Κ+; and Z- Any one of the following groups of ions: |〇s〇2cf3)·, (〇s〇2c4F9)_, (〇s〇AF), F (Να 4Ft} ^ (C(CF3)3 )-' (C(TM- ' (C(C4F9)3)-, F_, C1_, Br_, f, 叫, AsF6, and %. 7. A compound represented by the following formula 4: [Formula 4]? ?1 H2 H2 M+-°-|-?-c -c where in the formula 4 , Qi and Q2 each independently represent a halogen atom; X represents a group II group, an alkenediyl group, an NR group, an S group, an anthracene group, and a c group which are selected from the following groups: the alkane is not caused by a halogen atom and is burned. Among the ethnic groups formed by the basal group, the 丨中汉表44 201144264 ju-r / n represents an integer from 0 to 5; and M+ represents any one of the following groups of ions: Li+, Na+ And K+ 〇8. A chemically amplified photoresist composition comprising the photoacid generator according to any one of claims 1 to 5. 45 201144264 38471pif 4. Designated representative map: ( a) The designated representative of the case: No. (2) A brief description of the symbol of the representative figure: 命〇5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: [Formula 1] ί ?1 η2 η2 Α+ -Ο——S——C—C 一C—O 201144264 &lt; 38471pifl is the Chinese manual of No. 100118860. There is no slash correction. This article is dated: August 22, 2005. Instruction manual __, (The format and order of this manual, please do not change it at will, please do not fill in the ※ part) ※Application number: \〇. Other than 0 ※Application曰: Classification: 1. Invention Name: (Chinese/English) Photoacid generator and its manufacturing method and photoresist composition containing the same PHOTOACID GENERATOR, METHOD FOR manufacturing the same, and resist COMPOSITION COMPRISING THE SAME 2. Abstract of the Invention of the Invention: A photoacid generator represented by the following formula 1 and a method for producing the same, and a photoresist composition comprising a photoacid generator are provided. [Formula 1] Λ Λ 9 Η, H, ❹ A+ 爷—C—C, C —Ο 〇Q2, and 'Y denotes a group consisting of a cycloalkenyl group having a ring-burning group of 3 to 3G carbon atoms, Q and 卩2 each independently represent a halogen atom; any one selected from the group consisting of a column group: a divalent base, a 'NR', S, 0, C0, and combinations thereof; R, representing a hydrogen source | Any one of the selected groups; η means the whole of 〇 to 5: the soil shows organic relative ions. <登数, and Α+表1 201144264' 384/lpifl • For the Chinese manual No. 100118860, there is no slash correction. This revision period: August 22, 2010. VI. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a photoacid generator and a method of producing the same, and a photoresist composition containing a photoacid generator. More particularly, the present invention relates to a photoacid generator which is capable of generating an acid upon exposure, the acid having a low diffusion rate, a short diffusion distance, and exhibiting an appropriate acidity to achieve a line width roughness ( Line width roughness ; LWR) characteristics can be improved, and the dissolution in a solvent such as pure water used in the process can be controlled, and a method for producing a photoacid generator, and a photoresist composition containing a photoacid generator . [Prior Art] With the replacement of the micro-processing method using photolithography, a photoresist having a higher resolution is required, and in response to such a need, an amplification type resist is required. The amplified resist composition contains a photoacid generator. The photoacid generator in the chemically amplified photoresist composition is an important element' which imparts a chemically amplified photoresist to the resistivity and the photoresist composition in terms of riding, LWR, recording and the like. Therefore, a chemically amplified photoresist composition prepared by the study of various ray filaments, (10) was prepared. The nature of the field is very specific. Some properties of LWR and sensitivity characteristics. However, at the current level, 5 201144264 38471pifl is the Chinese manual of No. 100118860 without a slash correction - Revision date: August 22, 100. The modified chemically amplified photoresist is modified by the anionic portion of the photoacid generator. The study of nature is still insufficient. Based on the experimental data that reported that the anion moiety can exert greater influence on the physics and properties than the _ sub-portion, in fact, the nature of the f-stage composition, the new invention is about the anion moiety that has recently become true == ^. In addition, there is an increasing demand for photoacid generators that can simultaneously adjust the permeability. In addition, recently, the source of the chemically amplified photoresist needs to have a shorter wavelength than the commonly used g, line or i-domain, and thus the use of extreme ultraviolet radiation, KrF excimer laser light, A-beat laser light, Extreme ultraviolet (please) laser, X-ray and electron micro-shadowing were studied. In other words, since pure water is used for the exposure process in the immersion ArF method, the photo-curing composition for the N-type Al*F towel needs to have the following characteristics: The grade produces an acid from which the photoacid generator is not dissolved into pure water. SUMMARY OF THE INVENTION An object of the present invention is to provide a photoacid generator capable of generating an acid upon exposure, the acid having a low diffusivity, a short diffusion distance, and exhibiting an appropriate acidity to achieve a line width roughness (LWR) The characteristics can be improved, and the dissolution in a solvent such as pure water used in the process can be controlled. In order to achieve the above object, according to an embodiment of the present invention, a photoacid generator represented by the following formula 1 is provided: 201144264 JS4/lplfl is the first dirty imo number φ fiber duck thin line correction revision date·_1 August 22 Day [Formula 1] (V0 and 3/30 carbons on: from: a cycloalkyl group having 3 to 30 carbon atoms and i Γ and 0 = a selected group of women's groups - Qd Q2 Each of the individual iu also represents a functional atom; any one selected from the group consisting of 0 clusters. p f. alkyl, enediyl, NR, (d) h mountain and combinations thereof; R, represents a hydrogen atom and Any one of the constitutive groups; η represents an integer from 〇 to 5; and A+ represents an organic relative ion. According to another embodiment of the present invention, there is provided a method of producing a photoacid generator comprising the first step The compound represented by the following formula 8 is dissolved in a solvent, and the solution is reacted with a reducing agent to obtain a compound represented by the following formula 6; the second step: a compound represented by the following formula 7 is represented by the following formula 6 The compound is reacted in the presence of an inert catalyst to obtain a Q compound represented by the following formula 4 And a third step of subjecting a compound represented by the following formula 4 to a substitution reaction with a compound represented by the following formula 5, and thereby obtaining a compound represented by the following formula 1. 7 201144264 38471pifl No specification for the Chinese specification No. 100118860 Line correction date of this revision: August 22, 100 [Equation 8] 〇Qi u 0 · II r 1 Γΐ2 II Μ+ _0—S—C—C — C—O—Re 0 〇2 [Equation 6] M+ ^ i??1 H2 H2 -°~S-C-c -C -OH 〇2 II 0 [Formula 7] [Formula 4], - [Formula 5] [Formula 1] Λ ^ 9 ?1 h2 H2 A+- °~S—c—c ~C2- 〇q2 i, 5, Formula 6, Formula 7, and Formula 8, R6 represents 1 'Q2 Q5 each independently represents a halogen atom; and Y represents a cycloalkyl group of J and a nucleobase having 3 to 30 carbon atoms Among the ethnic groups, the stone, o, co and its group are dibasic, enediyl, eagle, R, and the atom and the alkyl group; η represents S, to 5 201144264 38471pifl. Revision period: 1 August The 22nd is the 10011 face number Chinese _ month book without the line correction of the integer; and A+ represents the organic relative ion. M+ represents any one selected from the group consisting of Li+, Na+, and K+; and Z_ represents any one of the following groups consisting of: (oso2cf3)~, (〇so2c4F9)- &gt; (〇S〇2C8F17)- ^ (N(CF3)2)- &gt; (N(C2F5)2)-, (N(C4F9)2) ^ (C(CF3)3)- . (C(C2F5) 3)- ^ (C(C4F9)3)- . F- &gt; Cl-, Br-, I-, BF4-, AsF6-, and PF6-. According to another embodiment of the present invention, there is provided a chemically amplified photoresist composition comprising a photoacid generator as described above. The invention will be described in more detail below. [Embodiment] The terms used in the specification of the present invention are defined as follows. The work is not specifically described in this article. Otherwise, the halogen atom means any one selected from the following groups: fluorine, chlorine, desert and strontium. (d) t ί text additional instructions ‘no listening base includes 'grade alkyl, secondary alkyl and tertiary alkyl. Deviation from two: Do not explain 'otherwise burned two bases by means of burning hydrocarbons. A divalent radical of in, and may be represented by the formula H, which is a radical of # from the upper of two hydrogen atoms and may be represented by the formula -CnHn-. Atom, otherwise a perfluoroalkyl group means a part of a hydrogen partial hydrogen; a substituted alkyl group, and an all-oxygen oxy group means a knife and an atom or a hydrazine, a substituted alkoxy group. After taking the special description, 'others' and the substituents may be used herein. The substitution means that the hydrogen atom has been corrected by the following 9 201144264 38471pifl as the Chinese manual of the 100118860. This revision date: August 22, 100 Any of the secret groups selected from the group consisting of the secret group, the thiolamine, the acne atom, the nitrile group, the thiol group, the epoxy group, the ether group, the methoxy group, the alkyl group , perfluoroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, derivatives thereof, and propyl 1 group, aryl unless otherwise specifically stated herein, otherwise ==three Group of choices; = unless otherwise specified herein, a straight or branched chain of a carbon atom; a diradical; a carbon atom; a dilute base means 2 to 1()^^;; allyl means an alkene having 2 to 1G carbon atoms, and an alkoxy group having 1 to ίο carbon atoms; a perfluoroanthracene to a total of 10 carbon atoms Burning base ·, perfluorodecyloxy means soil; there is a carbon atom of the whole city; the hydroxyl wire means that it has 丨 to (7) = a silk; a ring filament means an alkyl group having 3 to 32 carbon atoms, and a heterocycloalkyl group means a heterozygous jujube having 2 to 32 carbon atoms - meaning an aryl group having 6 to 30 carbon atoms; And a heteroaryl to a heteroaryl group of 30 carbon atoms. As used herein, Me is an abbreviation of fluorenyl. The photoacid generator of one embodiment of the present invention is represented by the following formula 1. [Formula 1] 〇Ql LJ U II I 1 H2 A+-0——S—C—C —C —〇O 〇2 n II丨10 X- €) 201144264 38471pifl No. 100118860 Chinese manual without underline repair! £This revised date beach material In the above formula 1, Q1 and Q2 each independently represent a halogen atom, and preferably a fluorine atom. η is an integer of 0 to 5, and preferably an integer of 〇 to 2. X represents a group consisting of the following groups Any one selected from the group consisting of: an alkanediyl group, an alkenediyl group, NR', S, fluorene, c〇, and a combination thereof, and R, which is selected from the group consisting of a hydrogen atom and an alkyl group. One may represent any one of the groups consisting of the following groups: Q -〇-' -〇CH2-' -OCH(Cl)- &gt; -C〇- &gt; -C0CH2- &gt; -COCH 2CH2- '-CH2-, -CH2CH2-, _CH2-0_, _CH2-〇_CH2-, -ch2ch2-o-, -CH2-0-CH2CH2- '-CH2CH2-0-CH2- '-CH2CH2CH2-O- ' -ch2-o-ch2ch2ch2-, -CH2CH2-〇-CH2CH2--CH2CH2CH2-0-CH2-. -CH(CH3)- &gt; -C(CH3)2CH2- &gt; -CH(CH3)CH2- ' -CH (CH2CH3)- '-CH(OCH3)---C(CF3)(OCH3)-, -CH2-S-, -CH2_S-CH2-, -CH2CH2-S-, -CH2-S-CH2CH2-, _CH2CH2- S-CH2-, -CH2CH2CHrS-, -CH2-S-CH2CH2CH2-, -ch2ch2-s-ch2ch2-, 〇-CH2CH2CH2-S-CH2-^-CH(CH2)CH- &gt; -C(CH2CH2)- &gt ; -CH2CO-, -CH2CH2CO-, -CH(CH3)CH2CO-, -CH(OH)-, -c(oh)(ch3)-, -CH(F)·, _CH(Br)_, _CH(Br CH(Br), -CH=CH·, -CH2CH=CH-, -CH=CHCH2-, _CH=CH_a, -CH=CH-S-', and _ch=CHCO-. In the above formula 1, Y represents any one selected from the group consisting of a cycloalkyl group having 3 to 30 carbon atoms and a cycloalkenyl group having 3 to 30 carbon atoms. 11 201144264 38471pifl is the Chinese manual of No. 100118860. There is no slash correction. The revision period: 1 8 8 η Y can represent any one of the following groups: Emery base, norbornene Norbornyl group, polycyclic cycloalkyl group having a norbornyl group having 1 to 3 carbon atoms, monocyclic cycloalkyl group having 3 to 14 carbon atoms, bicyclic ring having 4 to 20 carbon atoms An alkyl group, a tricyclic cycloalkyl group having 10 to 30 carbon atoms, and a tetracyclic cycloalkyl group having 1 to GO carbon atoms. One to five hydrogen atoms in the hydrogen atom of γ may be substituted by any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. a perfluoroalkyl group having 1 to 4 carbon atoms, a perfluoroalkoxy group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, a cyano group, a nitro group , amine, thio, thiol, decyloxy, OH, COR', and c〇〇R,. R represents any one selected from the group consisting of an alkyl group and an aryl group. Preferably, Y may represent any one selected from the group consisting of 丨-a to the following. 12 201144264 38471pifl Revision date: August 22, 1st is the Chinese manual No. 100118860. There is no slash correction [Equation 1-a] / ^&gt;Rn)a [Equation 1-b] b [Formula 1-c] [Equation 1-e] [式卜f] [式 l_g] 13 201144264 38471pifl is the Chinese manual of No. 100118860. There is no slash correction. This revision date: On August 22, 100, in the formula Ι-a to Ι-i, R11 and R12 each independently represent a hydrogen atom, an alkyl group, an alkoxy group. Base, perfluoroalkyl, perfluoroalkoxy, halogen atom, hydroxyl, carboxyl, cyano, nitro, amine, thio, methylthio, decyloxy, OR', COR', and COOR'. R represents any one selected from the group consisting of an alkyl group and an aryl group. In the above description, 'a, c and d each independently represent an integer from 〇 to 9; b represents an integer from 〇 to ;; e represents an integer from 〇 to 丨 5; and f represents an integer from 0 to 7; And 〇£C+d$17, and 〇$c+f$l5. Preferably, in the formulas a, Ι-b, Ι-d and ig, R11 may represent any one selected from the group consisting of a hydrogen atom, a burn having 1 to 6 carbon atoms. a group, an alkoxy group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, an all-gas burning having 丨 to 4 carbon atoms, a group having a secret of 1 to 6 carbon atoms Silk, halogen atom, thiol, cyano, nitro, amine, thio, methylthio, and methoxy. Further, in 1-c, 1-e, l_f, 14l, and Ui, each of the hydrogen atoms of the group consisting of the following groups may be independently represented: a hydrogen having 1 to 6 carbon atoms. a thiol group having one carbon atom, having a carbon atom of #1 to 4 fluorene, a fluorenyl group, a cyano group, a nitro group, an amine group, a thio group, a thiol group, an anthracene group, and combinations thereof. Preferably, the following formula 1-1 is selected from the group consisting of the group represented by the following formula 3 to 1-χχ, and the formula 3 is represented by the formula 1 The anionic portion of the compound. ',, 201144264 Revision period: August 21, 2017 38471pifl is the 10011818 Chinese manual without a slash correction [Form 3] -X- 9 ?1 h2 h2 -〇-s-c-c -c -o- )l IO 〇2 [Formula 1-i to 1-xx] o 〇Λ V 〇h2 [1-i] 9, f2 h2 h2 o f2 h2 ◦ , , CO o h2 -oo f2 h2 -,έ - Vcy ν' CC 〇h2 [1-iii] [1-iv] O F2 H2-0-WCV o h2 [1-ix ] 0 h2 No Myk 0 h2 3 ? Γ -o'® C, c/C, 0 person O H2 [1-x] [1-xi ] [1- Xii] ° c c2 Γ^τ°\ . -% C, c/C,. Human J 0 h2 -MKCr°r 〇h2 -crrC, cAo human 〇h2 [1-xiii] [1-xiv ] [1-xv] 〇f2 h2 I 0 F2 H2 -crVC,c/C,o〆0 h2 [1-xvi ] [l-xvii l ^ [1-xviii ] &gt;0H 15 201144264 38471pifi is the Chinese manual No. 100118860 without a slash correction. Amendment date: August 22, 100 〇 h2 OH [1-xx] When a light source such as ArF is used, the above photoacid generator obtained by introducing an alicyclic ring (aiiCyCiic ring) into the compound represented by the above formula 3 can provide an ability to adjust the acid diffusion rate and To exhibit a photoacid generator such as high ginseng, 沭彳q &amp; 士* / 边"王I will sign the part. From the anion ϋ of the compound represented by 3 to *1, A+ represents the organic relative ion. Lu Zhi, the selected component of the group consisting of the following formula 2, Α 2b can represent the cationic moiety of the compound of the following formula 2a and the formula 2. The formula 2 is represented by the formula 1 16 201144264 38471pifl :August 22, 100 is the Chinese manual No. 100118860. There is no slash correction. [Formula 2] A+ [Formula 2a] In the above formulas 2a and 2b, the core and each independently represent any one selected from the group consisting of a lower group: a hydrogen atom, a burnt group, a decano group, an all-(10) group, an aryl group, and combinations thereof, And RiA &amp; can be formed to form a saturated or unsaturated hydrocarbon ring having 3 to 3 carbon atoms. Any of the following groups of subgroups: a nitrite atom, a decyl group, an alkoxy group, an aryl group, an oxy group, a thiophenoxy group, and combinations thereof. The μ soil, the silk base, the base 3 and the R5 each independently represent any one selected from the group consisting of: a hydroquinone J group and a combination thereof. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, pentyl group and hexyl group from the propyl group, the aryl group, the aryl group and the two groups. And octyl, and the alkoxy group 17 201144264 38471pifl Revision date: hexyloxy on August 22, 1st, and the Chinese manual of No. 100118860 without scribe correction This example includes decyloxy, ethoxy, Propyloxy, butoxy, octyloxy. Further, the portion represented by the formula 2 may represent a cation portion of the compound selected from the group consisting of 2-χχ.斤述2 is a table of Formula 1 [Formula 2-i to 2-xx] [2-i] 12-ii ] [2-iv] [2-v] F [2-ix ] [2-iii ] I [2-χϋ ] 18 201144264 38471pifl Revision date: August 22, 1st year No. 100118860 Chinese manual without line correction [2-xvii ] [ 2-xviii ] [2-xix] S, ch3 [2-xx] The portion represented by Formula 2 may represent any one selected from the group consisting of the following formulas 3a and 3b, and the Formula 2 is a cationic moiety of the compound represented by Formula 1. 〇 19 201144264 38471pifl For the Chinese manual No. 100118860, there is no slash correction. Amendment date: August 22, 100 [Formula 3a] [Formula 3b] I + R3 In the formulae 3a and 3b, the core indicates that either one of the selected groups: a hydrogen atom, a group consisting of the following groups of a thiol group, and a combination thereof. A two-group, perfluoroalkyl group, aryl group, a group consisting of the following groups, an allyl group, a perfluoroalkyl group, an aryl group, R2 and &amp; each independently represents any one selected: a hydrogen atom, Alkyl groups and combinations thereof. I represents a sulphur atom, a decyl group, an alkoxy group, or an aryl group which is composed of the following groups: • an oxy group, a thiophenoxy group, and a combination thereof/channel group, a red group In 3a and 3b, examples of the alkyl group include an isopropyl group, a n-butyl group, a propyl group, a propyl group, and a octyloxy group having a f-oxy group, an ethoxy group, and a propoxy group. The butyl group has been reduced, and the other part represented by the formula 2 can be represented by the following formulas 3_i to ^ 20 201144264. The Chinese manual No. 1 &amp; 118860 is not underlined. This revision date: August 22, 100. Any one selected from the group consisting of the cation portion of the compound represented by Formula 1. [3-i to 3-ix] [3_i] [3-ii] [3-iii] [3-iv] [3-v] [3-vi] 3-vii ] [ 3-viii ] [ 3- Ix] A method of producing a photoacid generator represented by Formula 1 of another embodiment of the present invention includes: a first step: dissolving a compound represented by the following Formula 8 in a solvent, and reacting the solution with a reducing agent to obtain a lower portion a compound represented by Formula 6; a second step of reacting a compound represented by Formula 7 below with a compound represented by Formula 6 below in the presence of a basic catalyst to obtain a compound represented by Formula 4 below; and a third step A compound represented by the following formula 4 is subjected to a substitution reaction with a compound represented by the following formula 5, and thereby a compound represented by Formula 1 is obtained. The first step includes a process of dissolving a compound represented by the following formula 8 in a solvent, adding a reducing agent, and thereby obtaining a compound represented by the following formula 6. 21 201144264 38471pifl Revision date: August 22, 2011 is the 100118860 Chinese manual without a slash correction [8] 〇h2 0 M+ -OSCC -C-〇^R Ο 〇2 [Equation 6] ^ 9 91 h2 h2 M+ -0 —S—C—C—C—〇h II I 11 0 〇2 In Formulas 6 and 8, R6砉;, 岭 i Q The following groups are formed _ group towel selection = # From trimethyl sulfhydryl, tribromoindolyl, triiodoindolyl, ethyl, propyl, :: Q1 and Q2 each independently represent _ sound soil. It is expected that the group consisting of the following ions is a fluorogenic L-sub. Na+ and K+. Test .U+, for the dissolution in the first step reaction = any solvent can be used as long as the solvent can be dissolved by the formula 8: the cardinal reaction. ^丨起==(4) 'Allow (4) to ship down _ any of the constituents: ester, ether, lactone, hydrazine, decylamine: ground to remove the alcohol-based solvent and the following solvents: :Selection: =-者: Use: two gas, chloroform, dichloroethane group = sputum, tetrahydrofuran, dimethylformamide, dicarbonitrile, but the invention is not intended to be limited thereto. Solvent. The combination, = solvent can be a group consisting of the following alcohols: methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol,: 3 22 201144264 38471pifl is the 10011818 Chinese manual without line Amendment of this revision date: August 22, 100, butanol, oxybutanol, undecyl alcohol, decyl alcohol, heptanol, 2-mercapto-diterpene alcohol, allyl alcohol, ethoxy group Methanol, methoxyethanol, b-methoxy-2-propanol, (iv), phenylethyl alcohol, cyclohexanol, menthol, tetrahydro sugar alcohol, tetrachloroethylene alcohol, cyanobutanol, 4-base group 2-butanone, and combinations thereof, but the invention is not intended to be limited to such solvents. Any one selected from the group consisting of NaBH4, UA1H4, BH3-THF, NaBH4-AlC13, 0 NaBH4-LiCb LiAl(OMe)3, and combinations thereof may be used. The compound represented by Formula 8 and the reducing agent may be used in a molar ratio of 1:1 to 1:5, and preferably used in a molar ratio of 1:2 to 1:3.5. When the compound represented by Formula 8 and the reducing agent are used in the above molar ratio, the product yield with respect to the amount of the reducing agent to be used may be increased. Specifically, the first reaction may include the steps of dissolving the compound represented by Formula 8 in the above-mentioned solvent in an ice bath, adding a reducing agent to the solution dropwise to prepare a reaction mixture liquid, and flowing the reaction mixture liquid from Remove from the ice bath and heat and stir the reaction mixture liquid. The batching process is preferably carried out at 20 ° C to 120 ° C for 2 to 6 hours, and more preferably at 60 ° to 100 t for 3 to 5 hours. When the stirring process is carried out in the above temperature and time range, the product yield can be increased and by-product formation can be minimized. The reaction of the reaction mixture liquid is terminated by quenching to remove the solvent, followed by collection of the reaction product. Regarding the method of collecting the reaction product, any conventional method capable of removing the solvent from the liquid of the reaction mixture and collecting the reaction product can be used, and Example 23 201144264 38471pifl is the first 18_# Chinese manual without a sizing correction A method of curing a reaction product by using a recrystallization method, a mixture of a solvent which easily dissolves the obtained compound and a solvent which hardly dissolves the compound, a method of extracting the reaction product concentrate with a solvent, or concentrating on August 22 Method of reaction product. A preferred example of a method of collecting the reaction product that can be used is a method of removing a solvent from a liquid of a reaction mixture, dissolving the residue in distilled water, and then acidifying the solution to a pH of 5 to 6, and concentrating the reaction mixture: The liquid is again added to the concentrate to remove the inorganic salt in the form of a slurry, the residue is filtered, and the filtrate is crystallized using diethyl ether or the like. The compound represented by Formula 8 can be produced by the following steps: an intermediate preparation; / a reaction of a calcined oxide with a halide to form a dialkyloxy A compound having two alkoxy groups, followed by a second courtyard oxygen The two alkoxy groups of the group halide are oxidized to form a compound represented by the following formula 9; and the continuation step: reacting the compound represented by the formula 9 with an inorganic sulfite to form a compound represented by the formula 8. ^ [Equation 9] ?1 h2 〇Q3-C-C -c-〇-R6 q2 In the formula 9, R6 represents the yard base, and may specifically indicate any one of the groups consisting of the following group: Methyl, trifluoromethyl, tris; methyl, tribromomethyl, triiododecyl, ethyl, propyl, and butyl; and Q1 to Q3 each independently represent a halogen atom and are more a gas atom. In particular, the burned oxide used in the intermediate preparation step can be 24 201144264 38471pifl is the 10011818 Chinese manual without a slash correction. Amendment date: August 22, 2011, 3 to W carbon atoms The silk enamel contains a carbon-carbon double bond, and the specific substance may be methoxyethylene, ethoxyethylene or the like. The halide may be an alkyl halide and may specifically be perfluoromethane, dibromodifluoromethane, perbromomethane or perchlorodecane. 1. In the intermediate preparation step, the calcined oxide and the halide are reacted in an alcohol-based solvent. The compound may also react with sodium hydrogen sulfite (Na2s2〇4) and sodium hydrogen sulphate (NaHC(8). A specific example of an oxidizing agent which can be used in the presence of an oxidizing agent in the presence of an oxidizing agent and a oxidizing agent which is formed as described above is KHs〇5. Gl sodium hydride is used as the inorganic sulfite used in the renewal step, and the reaction can also be carried out after the addition of sodium hydrogencarbonate (NaHC^). When the sodium bisulfite is subjected to the catalytic reaction, it can be oxidized. The organic sulfonate thus formed produces a compound represented by Formula 8. In this case, hydrogen peroxide (H 2 〇 2), sodium tungstate (Na 2 W 4 ) or the like can be used as the oxidizing agent. The following procedure: a compound represented by the following formula 7 is reacted with a compound represented by the formula 6 in the presence of a basic catalyst and thereby a compound represented by the following formula 4 is obtained. 25 201144264 38471pifl No. 100118860 Correction The revised period: August 22, 100 [Expression 7] [Formula 4] ?1 H2 Hz / M+-〇-c - In Equation 4 and Equation 7, A, φ, (32^ atoms, and preferably a fluorine atom; and an independent integer from 0 to 2 in an independent manner. An integer of 5, and preferably M+ represents Li+, Na+, and K+ composed of the following ions. Any of the turtles. X and Υ It has the same as described above for the definition of the formula, and the definition will not be repeated. The compound is the same as the combination thereof. When the second step is carried out, the reaction of bis-ethyl isopropylamine is obtained in the minimum anti-riding (four) In the case of a silking agent, the yield can be obtained. The product is to be produced, and therefore, the reaction of the second step which can increase the reaction can be carried out in the solvent column _ group towel (4), and can be used as the following, _, As a solvent: vinegar, ether, a group consisting of the following substances: ground, the solvent may be dichloroethane, acetonitrile, methyl; di-methane, chloroform, acetaminophen, Acetate acetate, and its group 26 201144264 38471pifl is the first face number of the Chinese noodles without a slash correction. Amendment date: turn August 22 In the reaction, the compound represented by Formula 6 and the compound represented by Formula 7 may be used in a molar ratio of 1:1 to 1:3, and preferably may be used in a molar ratio of 1:1 to 1:1.5. When the compound represented by Formula 6 is reacted with the compound represented by Formula 7 in the above molar ratio, the two compounds can be completely consumed, and thereby the reaction efficiency can be increased. Further, in the reaction, the compound represented by Formula 6 The test catalyst Q can be used in a molar ratio of 1:1 to 丨: 4, and is preferably used in a molar ratio of 1:1.1 to 1:2. When the compound of formula 6 is used in an inert catalyst with the above-mentioned molar ratio, the reaction time can be accelerated and the removal of any residual organic catalyst can be made easier. The second step reaction may specifically include a process of dissolving a compound represented by Formula 6 and a basic catalyst in a solvent, stirring the mixture at an elevated temperature, and adding a compound represented by Formula 7 dissolved in a solvent to the mixture. Medium' and then the resulting mixture was stirred. The stirring process is preferably carried out at a temperature of from 4 ° C to 120 ° C for from 0.5 to 6 hours, and more preferably from 60 ° C to 9 (at a temperature of TC for 2 to 3 hours. When at the above temperature and time) When the stirring process is carried out within the range, the product yield can be increased 'and the formation of by-products can be minimized. The reaction of the liquid of the reaction mixture is terminated by quenching, the solvent is removed, and then the reaction product is crystallized. Thus, the formula can be obtained. The compound represented by 4. Regarding the crystallization method, any method can be used without limitation as long as the method is a common method of removing/treating the reactant from the liquid of the reaction mixture and crystallizing the reaction product. However, preferably, Washing the reaction mixture, followed by 27 201144264 38471pifl Revision date: August 22, 100 is the 100118860 Chinese manual without a slash correction. Separate the organic layer to remove the solvent, use column chromatography to separate the residue, then in a vacuum The reaction product is dried to obtain a reaction product. The second step includes the following procedure: substituting the compound represented by Formula 4 shown above with the compound represented by Formula 5 below And thereby obtaining a compound represented by the following formula 1. [Expression 5] A+Z- In Formula 5, Z- represents any one selected from the group consisting of: (〇so2cf3)-, ( 〇s〇2c4f9)-, (oso2c8F17)-, (N(CF3)2)-, (N(C2F5)2)-, (N(c4F9)2), (C(CF3)3)_, (C( C2F5)3)-, (C(C4F9)3)·, F-, Cl-, Br-, I-, BF4-, AsF6_ and PF0-; A+ represents organic relative ions. Due to the specific definition of this organic relative ion The definition given to the compound represented by Formula 1 is the same, and thus the description will not be repeated. The compound represented by Formula 4 and the compound represented by Formula 5 may be used in a molar ratio of 1:1 to 5:1, preferably 1 : 1 to 3:1 molar ratio is used, and even more preferably used in a molar ratio of 1:1 to 2: 1. When the compound is used in the above molar ratio, the reaction treatment time can be minimized and Any side reaction caused by the use of an excessive amount of the reaction product is suppressed. The substitution reaction may be carried out by using a recrystallization method, or a solvent which satisfactorily dissolves the salt (good solvent) and a poorly dissolved salt may be used. /Valent ( A mixture of poor binders is solidified and recovered from the reaction. 28 201144264 J〇*i·/ ipifl is the Chinese manual of No. 100118860. There is no slash correction. The date of this amendment: the method of salt obtained on August 22, 100, and A solvent extraction method, or a method of concentrating and recovering the obtained salt. Preferably, the compound is dissolved in dioxane and water to form two layers, which can then be stirred to cause a substitution reaction to take place. In the case of using such a two-layer reaction method, it is advantageous in that no other method is required to separate the product. Stirring can be carried out for 2 to 6 hours and can also be carried out for 2 to 4 hours. When the reaction is carried out in the above time range, the product yield can be maximized. When 0 is added to the compound represented by Formula 1 via the above procedure, the compound represented by Formula 1 can be produced by an efficient and simple method. The photoresist composition according to another embodiment of the present invention contains the photoacid generator represented by Formula 1 shown above. The photoresist composition is based on the composition of a conventional photoresist composition, and thus the description about the photoresist composition will not be repeated herein. The photoacid generator of the present invention can produce an acid upon exposure, the acid has a low diffusivity, a short diffusion distance 'and exhibits an appropriate acidity, a line width and a large slit (LWR) characteristic can be improved, and it is used in a process. Dissolution in a solution such as pure water can be controlled. Further, the method of producing the photo-developing agent of the present invention can produce the above-described photoacid generating stereotypes i by an efficient and simple method. The present invention will be described in detail by way of examples so that the present invention can be easily carried out by those having a technique of =2. However, the invention is described in the following: 1. The method of the present invention is limited to the photoacid generator 29 synthesized herein. 201144264 38471pifl is the Chinese manual of the No. 100118860. There is no slash correction. The revision date is: J. 22nd [Synthesis Example 1 of Photoacid Generator] Synthesis of adamantyl-3,3-difluoro-3-decyl-propyl bond diphenylmercaptophenylphene salt (Adamantyl-3,3-difluoro-3 -sulfo~propyl ether diphenyl methylphenyl sulfonium salt) (Step 1) As shown in the following Reaction Scheme 1, 83 g (0.376 mol) of 1,1-difluoro-3-methoxy-3- in an ice bath Sodium oxypropane-1-sulfonate was dissolved in 160 ml of methanol (MeOH) as a solvent and 1.2 liters of tetrahydrofuran (THF). 44 g (1. 16 mol) of sodium borohydride (NaBH4) was slowly added dropwise to the solution to prepare a reaction mixture liquid. After the dropwise addition was completed, the reaction mixture liquid was removed from the ice bath and heated to 60 °C. While maintaining the temperature, the reaction mixture liquid was stirred for about 4 hours. The reaction mixture liquid was quenched with distilled water, and then the solvent was removed. The crude reaction mixture was dissolved in distilled water' and the solution was acidified to pH 5 to 6 with concentrated hydrochloric acid. The acidified reaction mixture was concentrated and sterol was added thereto again. The slurry thus obtained was filtered to remove inorganic salts. The filtrate obtained by removing the slurry was washed twice with hexane, and the sterol layer was again concentrated, followed by crystallization using diethyl ether. The white solid obtained by crystallization was dried in vacuo, and the compound structure was determined by 1H-NMR. Thus, 65.8 g (〇. 346 mol; yield 95 ° / 〇 1,1-difluoro-3-hydroxypropane-1-sulfonic acid sodium. !H-NMR (D20): (ppm) 2.38 (t, 2H), 4.18(t, 2H) 30 201144264 38471pifl is the Chinese manual of No. 100118860 No picture dirty correction [Reaction flow 1] Revision period: August 22, 2005 NaBH4 Nao strange, Me - ° F2 g THF, MeOH Na 〇~〇H MeOH About Reference 'The 1,1-difluoro-3-indolyl-3-sideoxypropyl group shown above can be formed by a reaction such as the following Reaction Scheme 2 Burning 1-sodium pyruvate. 〇 [Reaction Scheme 2] OMe + CF2Br2 Na2S2〇4 F, NaHC03 B "One MeOH OMe OMe khso5 Br OMe N32S2〇4 NaHC03 Na02S 80C H2〇2 OMe Na2W04 Na03S OMe (Step 2) As shown in the following Reaction Scheme 3, 20 g (0.71 mol) of 1,1-difluoro-3-pyridyl-1-pyrene yellow formed in the step 1 was obtained. Sodium citrate and 23 ml (0.165 mol) of triethylamine (EhN) were dissolved in 400 ml of ethyl acetate, and the thus obtained solution was stirred at 80 °C. 5小时。 The reaction mixture was heated and stirred for 2.5 hours. The reaction mixture was stirred and stirred. After completion of the reaction of the reaction mixture, the reaction mixture was washed three times with 200 ml of a 1N hydrochloric acid solution, and the reaction mixture was washed once with 200 ml of a 1% by weight sodium chlorate solution. Separate the organic layer of the reaction mixture' and remove 31 201144264 38471pifl is the Chinese manual of No. 100118860 without a slash correction. The revised date is August 22nd. Solvent. The reaction product was separated by column chromatography using tannin and the reaction product was dried in vacuo. The dried reaction product was subjected to 1H_NMR' and the structure was confirmed. Thus, 30 g (yield 80%) of 3-(adamantan-1-yloxy)-1,1-difluoropropanin-1-sulfonic acid represented by the following formula A in Reaction Scheme 3 was obtained. Salt (3-(adamantan-l_yl〇Xy)_i, i_difluoropropane- 1-sulfonic acid salt) ° lH_NMR (dimethyl sulfoxide-form, tetramethyl decane): (ppm) 1.67-1.98 (m, 15H), 2.45 (t, 2H), 4.52(t, 2H) [Reaction Scheme 3] Cl Et3N Ο EA, 80 °C Na〇f C^^〇H + 〇F2 (Step 3) As shown in the following Reaction Scheme 4, The 8.5 g (0. 0255 mol) 3-(adamantyloxy)_1, 1_difluoropropane-1-sulfonate and 10 g (〇. 0234 mol) formed in the step 2 are The diphenylmethylphenylphosphonium trifluoromethanesulfonate represented by the formula B in the reaction scheme 4 is dissolved in 100 ml of dichloromethane/methylene chloride 'MC) and 1 ml of water to form two The reaction mixture of the layers. The reaction mixture was vigorously disturbed for 3 hours to allow the reaction (two-layer reaction) to proceed. When the stirring of the reaction mixture is completed, an aliquot of the organic layer is collected. 32 201144264 384/ipifl is the third 中文 Chinese manual without a slash correction. Amendment date: 1 kiss ribs Ο to check the reaction by 19f-nmr process. When the reaction is complete, the organic layer is collected and the solvent is removed. The digas methane was used as a good solvent and hexane was used as a poor solvent to wash the slurry obtained therefrom, and thereby a solid was obtained. The solid was dried under reduced pressure, and thereby the compound represented by the formula B in the following Reaction Scheme 4 was obtained. Thus, 13.3 g (yield 94.3%) of adamantyl-3,3-difluoro-3-yl-propyl ether diphenylmethylbenzene represented by the following formula C in Reaction Scheme 4 was obtained. Based on the salt, and the structure is determined by ih_NMr. h-NMR (chloroform oxime, tetradecyl decane): (ppm) i 67-1 98 (m, 15H), 2.45 (t, 2H), 2.47 (s, 3H), 4.76 (t, 2H), 7.48 ( d, 2H), 7.65-7.76 (m, 12H) [Reaction Scheme 4] NaO&quot; ?2~. Price ‘ o^_〇fc2~. ❺ Q ch3 B ch3 c Synthetic resin [Synthesis example 1 of resin] Add 3-bicyclo[2. 2.1]g-5-浠-2 to the molar ratio of hi :1 (33 parts: 33 parts: 33 parts) - Benzyl 3-hydroxypropionic acid tert-butyl ester, propyl acetonate 1-methyl Donkey Kong vinegar (acrylic acid 2-mercapto-2-gold sulphuric vinegar) and γ-butane oxime acrylate (acrylic acid) 2-sided oxytetrahydrofuran-3-yl ester), and the amount 33 201144264 38471pifl is the 10011818860 Chinese manual without a slash correction. The date of revision: (10) August 22 is equivalent to 3 times the total mass of the reaction monomer. 1,4 -dioxane is used as a polymerization solvent. Azobisisobutyronitrile in a ratio of 4 mol% based on the total molar amount of the monomer was used as an initiator, and the system was allowed to react at 65T: for 16 hours. After the reaction, the reaction solution was precipitated using n-hexane, and dried in a vacuum; Thus, a resin represented by the following formula 1 is obtained. The copolymer obtained in the form of a precipitate has a weight average molecular weight of 8,500. [Formula 10] Preparation of Photoresist [Comparative Example 1] - 1 part by weight of the obtained in the synthesis example of the resin was produced by the formula weight of 4 parts of trifluorof-sulfonic acid triphenyl age as photoacid (table BASE) 5 罝4微米膜过滤器过过。 The part of the tetramethylammonium hydroxide as an experimental additive (BASE) dissolved in 丨, the coffee weight of the diol (4) acetic acid solution through the 0.2 micron membrane filter. From this, a photoresist solution was prepared from ^ m ^ ^ ^ . The photoresist solution is applied to the substrate using a rotating ray, and the dry photoresist solution is entangled to a thickness of 90 seconds (10) m = excimer laser money H (Wei Kong Yu: G exposure, and heat treatment at 1 〇 for 9 sec seconds, Thus, the film p formed by the ruthenium is used for 丄38% by weight of hydrazine 34 201144264 38471pifl Revised date August 22nd is No. 100118860 Chinese specification No scribe line correction This tetra-ammonium aqueous solution develops the film thus formed for 4 sec seconds Then, the film was washed and dried. Thus, a photoresist pattern was formed. [Example 1] A photoresist solution was prepared in the same manner as in Comparative Example 1 except that 3 parts by weight of a synthetic example wipe was used and The adamantyl_3,3-difluoro_3_sulfo-propyl ether diphenylphosphonium basic sulfonium salt represented by the formula C in the process 4 is used as a photoacid generator. The properties of the photoresist solution are evaluated. Example 2] 'Photo resist solution was prepared in the same manner as in Comparative Example 1, except that 5 parts by weight of a diamond genus formed in the synthesis example 且 and represented by the formula C in Reaction Scheme 4 was used. , 3-difluoro-3-retentyl-propyl diphenyl nonylphenyl salt The photoacid generator was evaluated for the properties of the photoresist solution. [Example 3] 'Photo resist solution was prepared in the same manner as in Comparative Example 1, except that 7 parts by weight of the synthesis solution 1 was used and was reacted by the reaction scheme. The adamantyl-3, 3-difluoro-3-sulfo-propyl ether diphenylmethylphenyl sulfonium salt represented by the formula C in 4 is used as a photoacid generator. The properties of the photoresist solution are evaluated. 1 and the properties of Examples 1 to 3, such as sensitivity, resolution, and LWR, the results are presented in Table 1. In the case of LWR, the enthalpy formed after development was observed. 10/0. 10 μm line width/interval (line-and-space, L/S) pattern roughness, and the degree of improvement of LWR is divided into numbers of 1 to 5, and the pattern level obtained in Comparative Example 1 is 1. The larger number indicates 35 201144264 38471pifl For the Chinese manual No. 100118860, there is no slash correction. The date of this revision is: August 22, 2011. In the case of sensitivity, the line width/interval is 1:1 to form 0.10/0. The exposure amount of the 10 micron line width/space (L/S) pattern is specified as the optimum exposure amount' and will be When the sensitivity is set equal to the optimum exposure amount, the minimum pattern size obtained by imaging is specified as the resolution. [Table 1] Resin (100 parts by weight) PAG (η (parts by weight) base (2) (parts by weight) Sensitive Degree (min/joule decomposition (nano) 1〇~ ^WR~ Example 1 Synthesis of resin Example 1 3 0.5 17 Example 2 Synthesis of resin Example 1 5 0.5 16 1〇1 Example 3 Synthesis of resin Example 1 7 0.5 13 Λ . 70 3 Comparative Example 1 Synthesis of Resin Example 1 3 0.5 15 90 2 One (1) Photoacid Generator (PAG) Examples 1 to 3: were produced in Synthesis Example 1 and represented by Formula C in Reaction Scheme 4 Comparison of Example 1 : Triphenylsulfonium triflate (2) Alkaline Additive (BASE): Tetraammonium hydroxide was formed into the photoacid generator (PAG) used in Examples 1 to 3 by introducing an alicyclic ring into the anion of the photoacid generator. With the existing triflate or nonaflate photoacid generator phase 36 201144264 38471pifl Revision date: August 22, 2011 is the 100118860 Chinese manual without line The photoacid generator having a modified ratio of 'maintaining acidity similar to the acidity of the triflate salt has a low acid diffusion rate and a short diffusion distance. Therefore, the photoacid generator has characteristics suitable for realizing a finer L/S pattern. When the results of the analysis of the properties of Table 1 were studied, the photoacid generator exhibited superior performance in terms of LWR and resolution as compared with the existing trifluoromethane hydrochloride photoacid generator. When irradiated with light, introduction of an alicyclic ring into the anion of the photoacid generator exhibits excellent results even in terms of transparency. When the photoacid generates acid and the __ subform moves, the alicyclic ring does not affect the transparency at all, and the alicyclic ring size is determined to control the acid diffusion rate and diffusion distance. The beneficial effect. Therefore, the photoacid generator exhibits characteristics different from those of the existing photoacid generator. = The present invention is difficult to achieve the above, the county is the same as ^, and = the "any" key art, in the _ this day = within: when a little change and retouch, so the second invention: the scope is attached Those who are defined by the scope of application for patents are ashamed [simple description of the schema] ' ° [Signature description of main components] No 37 201144264 &lt; 38471pifl is the Chinese manual of No. 100118860 No underline correction This article is dated: August 22, 100 years Month ^ Invention patent specification __, (The format and order of this manual, please do not change it arbitrarily, please do not fill in the ※ part) ※Application number: \〇., other than 0 ※Application 曰: Classification: 1. Name of the invention: Chinese/English) Photoacid generator and its manufacturing method and photoresist composition containing the same PHOTOACID GENERATOR, METHOD FOR manufacturing the same, and resist COMPOSITION COMPRISING THE SAME 2. Abstract: A photoacid is represented by the following formula 1 a generating agent, a method for producing the same, and a photoresist composition comprising a photoacid generator. Λ Λ 9 Η, H, ❹ A+ 爷—C—C, C —Ο 〇Q2, and 'Y denotes a group consisting of a cycloalkenyl group having a ring-burning group of 3 to 3G carbon atoms, Q and 卩2 each independently represent a halogen atom; any one selected from the group consisting of a column group: a divalent base, a 'NR', S, 0, C0, and combinations thereof; R, representing a hydrogen source | Any one of the selected groups; η means the whole of 〇 to 5: the soil shows organic relative ions. <登数, and Α+表1 201144264 38471pifl is the Chinese manual of No. 100118860. There is no slash correction. This correction date: August 22, 100. The photoacid generator can generate acid upon exposure, and the acid has low diffusivity. Short diffusion distance and appropriate acidity to improve line width roughness characteristics. III. Abstract of the invention: There are provided a photoacid generator represented by the following formula 1, a method for manufacturing the same, and a resist composition comprising the same. [Formula 1] H1 h2 h2 A+ -O—S—C—C—C—〇II IO Q2 in the formula 1, Y represents any one selected from the group consisting of a cycloalkyl group having 3 to 30 carbon atoms, and a cycloalkenyl group having 3 to 30 carbon atoms; Q1 and Q2 each independently represent a halogen atom; X represents any one selected from the group consisting of an alkanediyl, an alkenediyl, NR', S, O, CO and combinations thereof; R' Any one selected from the group consisting of a hydrogen atom and an alkyl group; n represents an integer from 0 to 5; and A+ represents an organic counterion. The photoacid generator can produce, at the time of exposure, an acid which has a Low diffusion rate, has a short 201144264 J84/lpifl is the Chinese manual of the No. 100118860. There is no slash correction. The date of this amendment: August 22, the diffusion distance, and exhibits an appropriate of degree of acidity so that the line width roughness (LWR) characteristics can be improved. Q 3 201144264 38471pifl is the Chinese manual of No. 100118860. There is no slash correction. Revision date: August 22, 1 VII. Scope of application: 1. A photoacid generator, represented by the following formula [Formula 1] Λ ^ η Η 2 Η 2 Α + - 0 - S S - C - C - C - II I 〇〇 2 wherein in the formula 1, Y represents 3 carbon atoms having 3 to 3 G carbon atoms The structure _ _ _ has ^ Qi and Q2 each independently represents a halogen atom · X, selected from the group consisting of the following groups: π olefinic diyl, clothing, 8, 〇 &lt; 〇 and combinations thereof, Wherein one of the groups consisting of a ruthenium atom and a wire is selected; η represents an integer from 0 to 5; and Α+ represents an organic relative ion. 2. The photoacid generator according to item (i) of the medium-supply patent, wherein γ is not selected from the group of the following groups: diamond: 2 borneol, having 丨° to 30 carbon atoms Included in the base of the base of the base of the ice, a monocyclic group having 3 to 14 carbon atoms, a bicyclic ring group having 4 = 0 stone anatom atoms, and three having 1 to 3 carbon atoms 3 and % alkyl groups, and tetracyclic cycloalkyl groups having 1 to 3 carbon atoms. 3. The photoacid generator according to claim 1, wherein the Y table is not selected from the group consisting of the following formulas Ι-a to i-i: 38 201144264 J84/lpifl :100年月月22曰为第100118860号 Chinese manual without scoping correction [Formula l_a] y ^A&gt;Rn)a [式卜b] [Formula 1-c] [form l_d] [Equation 1-e] [Formula 1-f] [Formula 1-g] 5^Rll)e [Formula 1-h] 39 201144264 38471ρΐΠ Amendment date: August 22, 100 is the Chinese manual No. 100118860. There is no slash correction. In the above formula Ι-a to Ι-i, Rn and Rn can each independently form the following groups. Any one of the selected groups is substituted: alkyl, alkoxy, perfluoroalkyl, perfluoroalkoxy, halogen atom, hydroxyl, carboxyl, cyano, nitro, amine, thio, thiol , methoxy, OR', COR, and COOR, wherein R represents any one selected from the group consisting of an alkyl group and a square group; a, c and d each independently represent an integer from 〇 to 9; b denotes an integer from 〇 to 11; e denotes an integer from 0 to 15; f denotes an integer from 〇 to 7; and 0 S c+d $ 17, and 〇$ c+f $15. 4. The photoacid generator according to claim 1, wherein X in the formula 1 represents any one selected from the group consisting of: _0_, _OCH2-, _〇CH ( Cl)_, -CO-, -COCH2-, -coch2ch2-^-ch2- &gt; -ch2ch2- &gt; -ch2-o- ^ -ch2-o-ch2- ^ -ch2ch2-o-, -ch2-o -ch2ch2-, -ch2ch2-o-ch2-, -CH2CH2CH2-0-, -CH2-0-CH2CH2CH2-, -ch2ch2-〇-ch2ch2-, -ch2ch2ch2-〇-ch2-, -CH(CH3)-, - C(CH3)2CH2-, _ch(ch3)ch2-, _ch(ch2ch3)-, -CH(OCH3)·, -C(CF3)(OCH3)-, -CH2-S-, -CH2-S-CH2- -CH2CH2-S-, -CH2-S-CH2CH2-, -CH2CH2-S-CH2-, -CH2CH2CH2-S-, -CH2-S-CH2CH2CH2-, -CH2CH2-S-CH2CH2-, -CH2CH9CH2-S- CH2-, -CH(CH2)CH-, -C(CH2CH2)-, -CH2CO-, -CH2CH2CO-, -CH(CH3)CH2CO---CH(OH)---C(OH)(CH3)- , -CH(F)-, 201144264 38471pifl is the Chinese manual of No. 100118860. There is no slash correction. The revised period: August 22 曰-CH(Br)-, -CH(Br)CH(Br)- , -CH=CH-, -CH2CH=CH-, -CH=CHCH2-, -CH=CH-0-, -CH=CH-S-, and -CH=CHCO-. 5. The photoacid generator according to claim 1, wherein the portion represented by the following formula I represents any one of the following formulae 1-i to l_xx, wherein the formula 3 is The anion moiety of the compound represented by the formula 1 is: 〇[Formula 3] ° ?1 -C- 〇2[ΙΙ-i to 1 -〇-s-c1 ^ h2 , 'δ 4 C'°^X^) Χχ] q ι=2 ο 0 fi2 [1-i ] 0 F2 h2 %-〇C v sc 〇H2, 9 f2 h2 .义-〇,人 _ ◦ u CO 〇 h2 0 F2 h2 O-'s-C C〇 ^ w C 〇 0 H2 gamma [1-iv] -O o f2 W rT a o h2 [1-ix] q f2 h2 -os^c A υ Λ c C o h2 [1-X] xy〇H o f2 h2 O-'sC c'n w C 〇〇H2 [1-xi! 11-Xii ] 201144264 38471pifl No. 100118860 Chinese manual without line correction This revision date: August 22, 100 ° C Γ 2 Γ \^°\ ο h2 ° r /^V〇0 H2 [1-xiii] [1-xiv ] [1-XV 】 S h2 °t heart-( i 0 f2 h2 [1-xvi ] [1-xvii ] [1-xviii ] ϊ 0 f2 h2 ;\vc 0^ 0 h2 O Fo '' c w r Hd [1-xix ] 〇 h2 [1-xx] OH 6. A method of producing a photoacid generator represented by the following formula 1, the method comprising: a first step: dissolving a compound represented by the following formula 8 in a solvent, and reacting the solution with a reducing agent Obtaining a compound represented by the following formula 6; a second step of reacting a compound represented by the following formula 7 with the compound represented by the following formula 6 in the presence of a basic catalyst, and thereby obtaining a compound represented by the following formula 4; And a third step of subjecting the compound represented by the following formula 4 to a substitution reaction with a compound represented by the following formula 5, and thereby obtaining a compound represented by the following formula: Λ 42 201144264 38471pifl Revision period: August 22, 100 The Japanese manual No. 100118860 has no underline correction. [Equation 8] M+ &gt;-s-c-c - Ο 〇2 0-0-r6 [Equation 6] 91 h2 M+ -0-S-C-C - C -〇H Ο 〇2 〇ο [Formula 7] Qs—(-Χ- [Formula 4] II 1 〇〇2 [Formula 5] Α+Ζ- [Formula 1] Ο ?1 η2 η2 A+-0—S —C—C —C —〇— II I Ο 〇2 wherein in the formula 1, formula 4, formula 5, formula 6, formula 7, and formula 8, Han 6 is not burned; Qi, Q2, and Qs are each A halogen atom is independently represented; γ represents a group selected from the group consisting of a cycloalkyl group having 3 to 30 carbon atoms and a cycloalkenyl group having 3 to 10 carbon atoms, and is selected from the group of 43 201144264 38471pifl No. 100118860 The specification has no underline repair # Revision date: August 22, the second base group selected: - burned by the chlorine atom and the wire constructed by R, the table η represents an integer from 0 to 5; I, Α+ denotes organic relative ions; 胳 denotes Li+, Na+ and Κ+ composed of the following ions; and any of the wild rk: Z· represents the following ions (〇s〇2cF3)- ^ (oso2c4F9 (oso^r&quot;^ ' (C(C2F5)3). 7 A plugin BF4-, AsF6-' and PFfi 7. A compound represented by the following formula 4: (. (.4卩9) 3) -, F-, Cl-, Br~ (N(C2F5)2)., (N(C4F9)2) . (C(CF3)3) ((3)2)' [Formula 4] ΛΛ ^ i 1 H2 h2 ~c wherein, in the formula 4, γ represents a ring filament composed of 3 to 30 carbon atoms and 3 to Qi and Q2 each independently represents a halogen atom; —X represents Select one base from the group consisting of the following groups, and dilute Dibasic, NR, S, 〇, , , , 姨0, and combinations thereof, selected from the group consisting of oxygen atoms and alkyl groups in the pot; the medium is 44 201144264 38471pifl No. 100118860 Chinese specification without slash correction This revision date: η on August 22, 100 represents an integer from 0 to 5; and Μ+ represents any one of the following groups of ions: Li+, Na+, and Κ+ . A chemically amplified photoresist composition comprising the photoacid generator according to any one of claims 1 to 5. 45 201144264 38471pifl is the Chinese manual of No. 100118860. There is no slash correction. The correction date is August 22, 100. IV. Designated representative map: (1) The designated representative of the case: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: [Formula 1] Π 91 H2 H2 . A+-0—S—C—C —C —〇 —rXJn VYJ O Q2 n 4