TW520464B - Positive resist composition - Google Patents

Abstract

Provided is a positive resist composition with a view to improve the inherent performance of microphotofabrication using a far-ultraviolet light, especially ArF excimer laser light. Specifically, it has excellent sensitivity and resolution, and furthermore it may solve the problem that particle occurs in the resist solution with time. Additionally, provided is a positive resist composition which has excellent sensitivity and resolution, may solve the problem of development deficient occurring during the development, and provides a resist pattern having little density dependency. A positive resist composition comprises a specifically structured compound which generates an acid when exposed to an active light or radiation and has a specifically repeating structural unit and a specifically repeating structural unit containing an alicyclic ring in the backbone, and an acid-decomposable group.

Description

520464 A7 B7 V. Description of the invention (Technical field) The present invention relates to a method of using extreme ultraviolet as an exposure light source for ultra-microlithography engineering or other photoresist forming processes used in the manufacture of ultra-LSI or high-capacity microchips. A type of photoresist composition is, from another viewpoint, a positive photoresist composition using a far-ultraviolet range containing excimer laser light, particularly a wavelength of less than 220 nm, to form a high-definition pattern. [Prior art] In recent years, in order to further increase the integration degree of integrated circuits, it is necessary to process ultra-fine patterns with a line width of less than half a micrometer in the manufacture of semiconductor substrates such as ultra-LSI. To meet this need, the wavelength of exposure devices used in photolithography has been made shorter, and short-wavelength excimer laser light (XeCl, KrF, ArF, etc.) in far-ultraviolet light is also being reviewed. The pattern forming lithography user in this wavelength range is a chemically amplified resist. Generally speaking, the chemically amplified resists can be divided into three categories: 2-component system, 2.5-component system, and 3-component system. The two-component system is a combination of a compound that generates an acid by photolysis (hereinafter referred to as photoacid generation! J) and a binder resin. The binder resin is a resin which is decomposed by an acid and has a group (acid-decomposable group) which increases the solubility of the resin in the alkali developing solution in the molecule. The 2.5-component system contains a low-molecular compound having an acid-decomposable group in the 2-component system. The three-component system is one containing a photoacid generator, an alkali-soluble resin, and the aforementioned low-molecular compound. The above chemical amplification system is suitable for ultraviolet or far ultraviolet irradiation. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back? Matters and then fill out this page) 丨 Install- ------ Order --------- line

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 520464 A7 B7 V. Description of the Invention (2) Photoresist is used, but it must have additional characteristics corresponding to the requirements for use.

Ai * F photoresist composition for light source is proposed to introduce resins for alicyclic hydrocarbon sites for the purpose of having dry etching resistance. However, the disadvantage of the introduction of alicyclic hydrocarbon sites is that the system is extremely hydrophobic. It is known that the development of a tetramethylammonium cyanide (hereinafter referred to as TMAH) aqueous solution, which is widely used as a resist development liquid, is extremely difficult to develop, and phenomena such as peeling off from a substrate during development occur. Corresponding to the hydrophobization of the barrier, review the correspondence of organic solvents such as isopropyl alcohol in the developing solution. Although the effect can be seen, it is necessary to solve the problems such as the expansion of the barrier film or the complicated engineering. Most of the methods for improving the resistance have adopted a policy of introducing a hydrophilic group to compensate for each of the alicyclic hydrocarbon sites which are hydrophobic. Japanese Unexamined Patent Publication No. 10-10739 discloses a polymer containing a polymer obtained by polymerizing a monomer having an alicyclic structure such as an orthospinene ring in the main chain, a maleic anhydride, and a monomer having a carboxyl group. Energy sensitive barrier material. Japanese Unexamined Patent Publications No. 10- 1 1 1 569 and Japanese Unexamined Patent Publication No. 1 1-202491 disclose radiation-sensitive resin compositions containing a resin having an alicyclic structure in the main chain and a radiation-sensitive acid generator. The acid-decomposable group-containing resin used in the positive-type photoresist composition for far-ultraviolet exposure is generally one that contains both aliphatic cyclic hydrocarbon groups in the molecule. Therefore, the resin is hydrophobic, which is the cause of the problem. In order to improve this point and review the above-mentioned various methods, there are still a lot of inadequate points (especially in terms of imaging) in the above-mentioned techniques to improve. In other words, the resist composition is prepared as a solution by coating on the substrate, and after a period of time in the solution, a small amount of particles are generated, and there is a problem that the storage stability cannot be durable in use. -4- Too paper rule ;?谪 Use China National Standard (CNS) A4 specification (210 X 297 mm) installed --- (Please read the precautions on the back before filling this page)

I Printed by the Employees 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 520464 A7 __ B7_ V. Description of the Invention (3) In addition, the above far ultraviolet light, short-wavelength light source, such as ArF excimer laser (193nm) As a technology of exposure light source, the image development property still needs to be improved. Specifically, there is a problem that a development defect occurs. In addition, there are still issues that need to be improved regarding the relevance of sparseness. The tendency of the instrument is that it contains various patterns and requires various properties of the blocking body. One is the density of correlation. There are line-dense parts in the instrument, and there are patterns that are wider than the lines, and isolated lines. Therefore, it is extremely important to have various lines with high reproducibility and resolution. However, it is extremely difficult to make various line reproductions by optical factors, and the current solution by a resistive body is not clear. Especially in the resistance system containing the above alicyclic base, the performance difference between the isolated pattern and the dense pattern is extremely significant, and an improvement is sought. [Disclosure of the invention] The purpose of the present invention is to provide a method for using ultra-ultraviolet light, especially ArF excimer laser light, to solve the above-mentioned problem of improving the original performance of the photoresist molding process, and in particular, to provide a sensitivity, that is, an excellent resolution, The positive photoresist composition can solve the problem that particles are generated in the resist solution after a period of time. The second object of the present invention is to provide a method for using extreme ultraviolet light, especially ArF excimer laser light, to solve the above-mentioned problem of improving the original performance of the photoresist molding process. Specifically, it is to provide an excellent sensitivity, that is, a high resolution, which can be solved in A positive-type photoresist composition that causes development defect problems during development. Another object of the present invention is to provide a regular photoresist composition having a small density and a small density, and an excellent resistive pattern. The inventors have repeatedly studied the photoresistance of the positive chemical amplification system. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Packing-(Please read the note on the back? Matters? (Fill in this page) 520464 A7 B7 V. Description of the invention (4) As a result of the agent composition, it was found that by using a specific photoacid generator and a specific acid-decomposable resin, and by combining a specific acid-decomposable resin and a specific structure The photoacid generator and specific surfactant can achieve the first purpose of the present invention. In addition, by combining a specific acid-decomposable resin with a photoacid generator with a specific structure and a specific surfactant, the cost can be reached. The second purpose of the invention was achieved by the invention. In other words, the above object is achieved by the following constitution. (1) A positive-type photoresist composition characterized by containing (A) at least one compound selected from the compounds represented by the following general formulae (I) and (II) that generates an acid by irradiation with active light or radiation, And (B) has at least one selected from a repeating unit represented by the following general formula (IaJ and general formula (lb ')) and a repeating unit represented by the following general formula (II'), and has an action by an acid Decomposed polymer. --Pack-(Please read the note on the back? Matters before filling out this page). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

—6- This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) 520464 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (5) (Formula (I)-(II ), Ri to R27 each represent an independent hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom, or -S -R28 group; r28 is a linear, branched, or cyclic alkyl or aryl group; but at least one of R15 ~ R15 ~ R27 is not a hydrogen atom; and Ri ~ R15, R16 ~ R27 In the above, two or more kinds of bonds may be formed to form a ring containing one or two or more kinds selected from single bonds, carbon, oxygen, sulfur, and nitrogen; X- is represented by RFS03_; wherein, RF is fluorine-substituted with 2 or more carbon atoms. Linear, branched, or cyclic alkyl) o = cc: o IIXXI Ift (la,) i I ~ " (? ~~ ρ ~ (II,) (In formula (la '), R'rRS , Each represents an independent hydrogen atom, cyano, hydroxyl, -COOH, -COOR, 5, -CO-NH-R ,, C0-NH-S02-R'6, substitutable radicals, radicals Or a cyclic hydrocarbon group, or the following _ γ group; Substitutable alkyl group, cyclic hydrocarbon group or the following _Y group; R'6 is a substituted alkyl group or cyclic hydrocarbon group; -7-

This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) • Loading --- (Please read the precautions on the back before filling this page) »· Line! 520464 V. Description of the invention (X represents a oxygen atom, a sulfur atom, -nh_ A represents a single bond or a divalent linking group; -Y is

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs NHS02-or-NHS02NH ·

(Wherein 'each represents an independent hydrogen atom or an alkyl group which may have a substituent, and a, b represents 丨 or 2); In the formula (lb), Z2 represents -0_ or _n (r, 3) _ (Where 'R'3 represents a hydrogen atom, a hydroxyl group or _〇s〇2_r, 4; r, 4 represents an alkyl group, a halogenated alkyl group, a cycloalkyl group or a camphor residue); in the formula (Plant 1), R'll 'R'12 each represents an independent hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent; Z is a group which contains two carbon atoms (CC) to form a substituent Alicyclic structure atomic group) (2) a positive photoresist composition, characterized in that it contains, (A) at least one selected from the following general formula (IB) and The photoacid generator of the compound represented by (IIB), (B) has at least one repeating unit selected from the following general formula (la ') and general formula (lb') and the following general formula (II ') The polymer shown in the repeating unit and having a group decomposed by the action of an acid, and (C) a fluorine-based and / or silicon-based surfactant. This paper size applies to China National Standard (CNS) A4 size mo X 297 mm) (Please read the precautions on the back before filling this page)

520464

5. Description of the invention (

b X · (IB) Q 〇ύ 5

2X (IIB) (In the formulae (IB) to (IIB), X · represents RFS03 ·; wherein RF is a linear, branched or cyclic alkyl group substituted with fluorine having a carbon number of 2 or more) i— — (Please read the notes on the back before filling this page) 5J »Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs— " (CH—Cl ^-o = c I c = o 1 1 X 1 1 XI 1 AI 1 AI 1 Ri r2 (I a,) wide: / 1 1 z ,, \ 1 ten + R11 r12,), h, CH-CH—

(I b,) (in • COOH, -COOR5, -CO-NH-R6, -C0-NH-S02-R6, a p group which may be substituted, an alkoxy group or a cyclic hydrocarbon group, or a -Y group described below ; X means oxygen atom, sulfur atom, -NH-, -NHS02- or -NHS〇2Nh, this paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 520464 employee consumption of Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative prints A7 B7 5. Description of the invention (8); where 'I represents a substituted alkyl, cyclic hydrocarbon group or the following _γ group; R6 represents a substituted alkyl or cyclic hydrocarbon group; A Is a single bond or a divalent linking group; -Y is

(Wherein R21 to R3Q each represent an independent hydrogen atom or a substituent which may have a substituent, a and b represent 1 or 2); in the formula Ub ·), Z2 represents -0- or -N (R3) -(Wherein R3 represents a hydrogen atom, a hydroxyl group, or 〇〇〇2-R4; 1-4 represents an alkyl group, a halogenated alkyl group, a cycloalkyl group or a camphor residue); in the formula (II㈠,

Rn and R12 each represent an independent hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent; Z is a cycloaliphatic structure containing two carbon atoms (CC) to form a substituent (3) The positive photoresist composition according to the above (1) or (2), wherein the repeating unit represented by the general formula (II ′) is the following general formula (IΓ-A ) Or a repeating unit represented by the general formula (Π'-B).

~ R.15M (ΙΓ-Α) Ul'-B) This paper size is applicable to China National Standard (CNS) A4 (210 x 297 mm) ------------- 05 .-- (Please read the note on the back before filling out this page)

520464 A7 B7 I. Description of the invention (9) (wherein in formulas (II'-A) and (II, B), R'13 to IT16 are each independently hydrogen atom, halogen atom, cyano group, -C00H,- COOR'5 (R'5, synonymous with the above), a group decomposed by the action of acid, -c (= o) -xa-r'17, or an alkyl or cyclic hydrocarbon group which may have a substituent; and IΓ13 ~ ΙΓ16 are bonded to form at least two rings; here, X and A are each synonymous with the above; R'17 is -C00H, -COOR'5, -CN, cyano, and alkoxy which may have a substituent Group, -C0-NH-R, -C0-NH-S02-R, (RS, each is synonymous with the above) or the -Y group; η represents 0 or 1;) (4) as described above ( 1) The orthophotoresist composition according to any one of (3), wherein the rf of X · in general formulae (I) and (II) is based on CF3 (CF2) y (wherein y is It is an integer of 1 to 9) and a fluorine-substituted linear alkyl group. (5) The positive-type photoresist composition according to any one of (1) to (4) above, wherein y is an integer of 1 to 7. (6) The positive-type photoresist composition according to any one of (1) to (5), wherein y is an integer of 1 to 4. --- (Please read the precautions on the back before filling out this page) 口 ， 1. | Line · Printed by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (7) As described in (1) or (3) ~ (6) above The positive-type photoresist composition according to any one of the components, wherein the component (A) is a compound having the following structure.

-11- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 520464 κι — ---- B7__ V. Description of the invention (10) (where X · is synonymous with the above) (8) As in any of the above (2) to (6) The positive-type photoresist composition according to one item, wherein the (A) photoacid generator is a compound represented by the following formula. CF3 (CF2) 3S〇3 (9) The positive type photoresist composition according to any one of (1 to 8) above, further containing a nitrogen-containing basic compound. (10) As described in (1) or ( 3) The positive photoresist composition according to any one of (9), which contains a fluorine-based and / or silicon-based surfactant. (11) As described in any of (1) to (10) above The positive-type photoresist composition according to the item is used for irradiation of active light or radiation with a wavelength of 220 nm or less. (Embodiment of the Invention) The first positive-type photoresist composition of the present invention will be described in detail below. The compound used in the product and the method of using the composition, etc. [1] (A) The photoacid generator used in the present invention is a compound (photoacid generator) that generates an acid by irradiation with active light or radiation. The photoacid generator of the present invention uses at least one of the compounds represented by the general formulae (I) and (II) above. In the general formulae (I) to (II), straight chains and branched chains of 1 to 27 and R28. The alkyl group has, for example, methyl, ethyl, propyl, and n-butyl which may have a substituent. 12- This paper is in accordance with China National Standard (CNS) A4 (21 0 X 297 mm) (Please read the notes on the back before filling this page)

520464 Printed by A7 B7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs 5. Description of the invention (1, 4 carbon atoms such as phenyl, 2-, 2-, and 3-butyl. Cyclic alkyl may be substituted, for example Cyclopropyl, cyclopentyl, cyclohexyl, and the like have 3 to 8 carbon atoms. R 1 to R 2 7 are straight-bonded and branch-bonded ethoxy groups such as methoxy and ethyl which may have a substituent. 1 to 4 carbon atoms such as oxy, hydroxyethoxy, propoxy, n-butoxy, isobutoxy, 2-butoxy, and 3-butoxy. Cycloalkoxy is The cyclopentyloxy group includes, for example, a cyclopentyloxy group and a cyclohexyloxy group. Examples of the halogen atom having 1 to 27 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. An aryl group of R28 includes a phenyl group and toluene Carbonyl, methoxyphenyl, naphthyl and the like having 6 to 14 carbon atoms which may have a substituent. These substituents include 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, iodine). Atoms), 6 to 10 carbons, aryl groups, 2 to 6 carbons, cyano, triphenyl, end, residue carbon, nitro, etc. In addition, there can be more than 2 bonds in Ri ~ R15 Knot formation contains 1 type or more The ring from a single bond, carbon, oxygen, sulfur, and nitrogen is, for example, a furan ring, a dihydrofuran ring, a pyran ring, a trihydropyran ring, a thiophene ring, or a pyrrole ring. The same applies to R16 to R27. General formula ( In I) to (II), X · represents an anion shown in RF-S03 ·. Among them, 'RF represents a carbon number of 2 or more, preferably 2 to 10, more preferably 2 to 8, and most preferably Fluorine-substituted linear, branched, or cyclic courtyards of 2 to 5. -13- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the back (Please fill in this page again)

520464 Printed by A7 in the Consumer Property Cooperative of the Intellectual Property Bureau of the Five Ministry of Economics. (12) The preferred RF is represented by CF3 (CF2) y, where y is a fluorine-substituted linear alkyl group with an integer of 1-9. It is preferably an integer of 1 to 7, and more preferably a fluorine-substituted linear alkyl group of 1 to 4. By using such a fluorine-substituted linear alkyl group (CF3 (CF2) Y), the balance of sensitivity and resolution is excellent, and the change in performance over time even after exposure to heating is small. Specific examples of RF include CF3CF2 ·, CF3 (CF2) 2 ·, CF3 (CF2) 3_, cf3 (cf2) 4 ·, cf3 (cf2) 5 ·, CF3 (CF2) 6-, cf3 (cf2) 7 ·, cf3 ( cf2) 8 ·, cf3 (cf2) 9_ are better, more preferably cf3 (cf2) 3 ·, cf3 (cf2) 7 ·, and the best is CF3 (CF2) 3 ·. A more preferable photoacid generator is a compound represented by the general formula (I), in which each benzene ring of the cation part is substituted with a 3-butyl group, and X · is CF3 (CF2) 3S03_. good. By using a compound represented by the general formulae (I) to (11) composed of a sulfonic acid anion having a fluorine-substituted alkyl group in the anion part as a photoacid generator, and combining the resin component (A) of the specific structure described above, The positive photoresist composition of the present invention has sufficient sensitivity and resolution for exposure to far ultraviolet light, especially ArF excimer laser light (wavelength 193 nm), and can maintain excellent performance over time after exposure. Pattern appearance and resolution. Specific examples of the photoacid generators represented by the general formulae (I) to (11) include the following compounds (1-1) to (1-27) and (II-1) to (Π-7). -14- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

520464 A7 B7 V. Description of the invention (Η

S + CF3 (CF2) gS〇3 (1-5)

QrK

Cl CF3 (CF2) 7S〇3

S ^ CF3 (CF2) 3S〇3 3 (1 ~ 2)

S + CF3 (CF2) 7SO:

Cl 3 (1-4)

CF3 (CF2) 3S〇3 (Please read the precautions on the back before filling this page)

(1-6)

Cl

t-Bu

QrL CF3 (CF2) 3S〇3 一

Cl (1-7)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs t-Bu

CF3 (CF2) 7S〇3 o- t-Bu (Bu 9) t-Bu (1-8) t-Bu

s + CF3 (CF2hS〇3

(1-10) • 15 · This paper size applies to China National Standard (CNS) A4 (210 x 29V mm) 520464 A7 B7 V. Description of the invention (κ)

t-Bu

CF3 (CF 2) 7 ^^ 3 CF3 (CF2): 3S〇3

(1-11)

m

CF3 (CF2) 5S〇3 H3CO

Or

(1-12) Cl

(Please read the notes on the back before filling this page)

H3CO (M3) Cl

H3CO —

s + cf3 (cf2) 3s〇3

(M6) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

CF3 (CF2) 3S〇3 (1-18) • 16- This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 520464 A7 B7 V. Description of the invention (

EtO CF3CF2SO; (1-19)

CF3 (CF2) 3S〇3 (I-20)

〇 卞

CF3 (CF2) 5S〇3 (1-21) (I-22)

(Please read the notes on the back before filling this page)

< Q ^ S-hQ > -S / + CF ^ CF ^ SOa

S + CF3 (CF2) 3S〇3 (I-24)

S; CF3 (CF2) 7S〇3 (I ~ 25)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

HO

• 17 · (I-23)

This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 520464 A7 B7 V. Description of the invention (々

S 2 CF3 (CF2) 3 ^^ 3

S 2 CF3 (CF2) 9S03- S 2 CF3 (CF2) 3S〇3 一 i --- (Please read the precautions on the back before filling this page) Line ·

Cl Printing of clothing by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

S 2 CF3 (CF2) 5S03 一 -18- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

S 2 CF3 (CF2) 3S〇3-

S 2 CF3CF2S〇3

S

S 2 CF3 (CF2) 3S03- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs as shown in the above general formulae (I) and (II) (A) The amount of photoacid generator added is based on the solid content of the photoresist composition The basis is usually 0.001 to 40% by weight, preferably 0.01 to 20% by weight, and more preferably 0.1 to 5% by weight. If the amount of the photoacid generator is less than 0.001% by weight, the sensitivity is low, and if the amount is more than 40% by weight, the light absorption of the resist is too high, the appearance is not good, and the engineering (especially baking) range is narrow. Not for desire. -19- (Please read the notes on the back before filling this page)

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 520464 A7 B7__ 5. Description of the invention (18) Next, the detailed description of the second invention is A compound used in the photoresist composition and a method of using the composition. [1] (A) The photoacid generator used in the present invention is a compound (photoacid generator) that generates an acid by irradiation with active light or radiation. The photoacid generator of the present invention uses at least one compound represented by the general formulae (IB) and (IIB). In the general formulae (IB) to (IIB), X · represents a negative ion represented by Rf-S03 ·. Among them, RF refers to a fluorine-substituted linear, branched, or cyclic radical having a carbon number of 2 or more, preferably 2 to 10, more preferably 2 to 8, and most preferably 2 to 5. The preferred RF is represented by CF3 (CF2) y, where y is a fluorine-substituted linear alkyl group having an integer of 1 to 9, preferably an integer of 1 to 7, and more preferably 1 to 4 of fluorine. Substituted linear alkyl. By using such a fluorine-substituted linear alkyl group (CF3 (CF2) y), the balance of sensitivity and resolution is excellent, and the change in performance over time even after exposure to heating is small. For example, CF3CF2 ·, CF3 (CF2) 2 ·, CF3 (CF2) 3 ·, CF3 (CF2) 4-, CF3 (CF2) 5 ·, CF3 (CF2) 6-, CF3 (CF2) 7-, CF3 ( CF2) 8 ·, CF3 (CF2) 9 · are better, more preferably CF3 (CF2) 3-, CF3 (CF2) 7_, and the best is CF3 (CF2) 3 ·. A more preferable photoacid generator is a compound represented by the general formula (IB) where Γ is CF3 (CF2) 3 S03_, that is, a compound represented by the following specific example (IB-2). By using a compound represented by the general formulae (IB) to (IIB) composed of a sulfonic acid anion having a fluorine-substituted alkyl group in the anion part as a photoacid generator, the resin component (A) having the specific structure described above is combined. And with ~ 20- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -----— II --- I-- · II (Please read the precautions on the back before (Fill in this page)-Line-520464 A7 _ Β7 ^-~~ ---- 5. Description of the invention () Combination of (A) acid-decomposable resin with specific structure below and (C) fluorine-based and silicon-based interface An active agent, the positive photoresist composition of the present invention has sufficient sensitivity and resolution for exposure to far ultraviolet light, especially ArF excimer laser light (wavelength 193 nm), and can be used for the time after exposure. It maintains excellent pattern appearance and resolution, and can substantially solve the development defects generated during development, and has excellent density and correlation. Specific examples of the photoacid generators represented by the general formulae (IB) to (IIB) include the following compounds (IB-1) to (IB-5), (IIB-1) to (IIB-5). --Installation --- (Please read the precautions on the back before filling this page) · Λ Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with China National Standard (CNS) A4 (210 X 297 mm) 520464 A7 B7 V. Description of the invention (CF3CF2SO3 I B-1) CF 3 (CF 2) 3 ^ 03 (I B-2) (0) rs 'CF3 (CF2) 5S〇3 (IB-3) (Ots' CF3 (CF2) 7S〇2 (I B-4)

s CFaiCF ^ gSOa (IB-5)

• s 2 CF3CF2SO3 --Install --- (Please read the notes on the back before filling this page) --Line Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

S 2 CF3 (CF2) 3S〇3- (ΠΒ-2) -22- The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) 520464 A7 B7 21 V. Description of the invention ()

• S 2 CF3 (CF2) 5S〇3- (IIB-3)

S 2 CF3 (CF2) 7SO;

S 2 CF3 (CF2) 9S〇3 Printed by the above-mentioned general formulae (IB) and (IIB) (A) Photoacid generator is added in the amount of the solid content of the photoresist composition. As a reference, it is usually 0.001 to 40% by weight, preferably 0.01 to 20% by weight, and more preferably 0.1 to 5% by weight. If the amount of the photoacid generator is less than 0.001% by weight, the sensitivity is low, and if the amount is more than 40% by weight, the light absorption of the resist is too high, the appearance is not good, and the engineering (especially baking) range is narrow. Not for desire. The positive photoresist composition of the present invention can be used in addition to the above general formula -23. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling (This page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 520464 A7 _B7__ 22 V. Description of the Invention (I), (II), (IB), (IIB) Photoacid generators other than the compounds shown in (I), (II), (IB), (IIB). The compounds used in the present invention to generate an acid by irradiation with active light or radiation can be appropriately selected using a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photochromic agent for pigments, and photochromism. Conventional light used by agents or microresistors (400 ~ 200nm UV, especially g-line, h-line, I-line, KrF excimer laser light), ArF excimer laser light, electron beam, X-ray, molecular beam or Ion beam to generate acid compounds and select these mixtures appropriately. In addition, other photoacid generators that can be used include, for example, azo iron salts, ammonium salts, phosphonium salts, iodine salts, sulfonium salts other than the above, selenium salts, arsenic salts, organic halogen compounds, Organometallic / organic halides, photoacid generators with ortho-nitrobenzyl-type protective groups, iminosulfate and other typical photodecomposition compounds that produce sulfonic acids, two-mill compounds, diazolone maple, Diazo dimill compounds and so on. In addition, compounds which generate an acid group by light or introduce a compound into the main or side chain of a polymer may be used. In addition, V.N.R.Pi 11a 1, Synthesis, (1), 1 (1 980) can be used.

I. A. Abad etal, Tetrahedron Lett., (47) 4555 (1971), DHRBarton etal, J. Chem. Soc, (C), 329 (1970), U.S. Patent No. 3,779,778, European Patent No. 126,712 The compound described in No. etc. generates an acid by light. Particularly effective among the above-mentioned compounds that generate acid by irradiation with active light or radiation, for example, the following general formula (PAG3), general formula (PAG4), -24- This paper size applies the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) (Please read the precautions on the back before filling out this page) Loading -------- Order --------- Line ----------- .--- 520464 A7 B7 23 V. Description of the invention (Compounds represented by general formula (PAG6) or general formula (PAG7).

At *

R, 203

Z R204—δΘZZΘ

Ar2 (PAG3) R205 (PAG4)

Packing --- (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (general formula (PAG3), (PAG4), Ar1, Ar2 are independent replacements Or an unsubstituted aryl group. Preferred substituents include, for example, an alkyl group, a halogenated alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a residue, an alkyloxycarbonyl group, a hydroxyl group, a thiol group, and Halogen atom. R2 03, R2 (H, R205) each represents an independently substituted or unsubstituted academic group or aryl group. Preferred are aryl groups having 6 to 14 carbon atoms and 1 to 8 carbon atoms. Alkyl and these substituted derivatives. Preferred substituents for aryl are alkoxy having 1 to 8 carbons, alkyl having 1 to 8 carbons, nitro, carboxyl, meridian, and halogen. Atoms, for alkyl groups, have alkoxy groups, residues, and oxo groups with 1 to 8 carbon atoms. Z_ represents a counter anion, such as 8? ^, 8? 6- ?, ?? 6-, 35? 6-, > C104_ 'CF3SCV, Alkylsulfonic acids that can be substituted, Perfluoroalkanesulfonic acids, benzenesulfonic acids that can be substituted, naphthalenesulfonic acid, anthracenesulfonic acid, camphorsulfonic acid, etc. However, the present invention is not limited by these . Preferred are alkane sulfonic acid, perfluoroalkane sulfonic acid, benzene sulfonic acid which can be substituted, pentafluoro-25. _ ^ (CNS) A4 size (210x 297 mm) Order--line · 520464 A7 B7__ v 24 V. Description of the invention () benzenesulfonic acid. Moreover, at least two of R2 () 3, R2 ° 4, R2Q5 and Ar1 and Ar2 may each be a single bond or a substituent bond. In the general formulae (PAG6) and (PAG7), R2Q6 represents a substituted or unsubstituted alkyl group or an aryl group. A represents a substituted or unsubstituted alkylene group, an alkenyl group, or an arylene group. R represents a linear, branched, or cyclic alkyl group, or an aryl group which may be substituted) These specific examples include the following compounds, but the present invention is not limited by them. — — — — — — — — II (Please read the precautions on the back before filling out this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) ) 520464 A7 B7 V. Description of the invention (<) + α- · Θ-ο CF3SO3 Θ (PAG3-1)

Θ \

(PAG3-3)

Of

F_V / ~ so F F S® CF3SO3 Θ Θ 3 (Please read the precautions on the back before filling this page) (PAG4-1)

Θ

3 (PAG4-2) S〇 ^ S Θ

F

S03 0

(PAG4-3) F F Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy (PAG4-4)

Θ Θ «This paper size is in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm) 520464 κι. Β7 5. Description of the invention (26. 〇

Of OBu

COOBu s © C ^ S〇30 (PAG4-5) 〇 N—O—S〇2—CF3

O (PAG6-1)

Installation-(Please read the note on the back? Matters before filling out this page) 〇

— · O-S〇2-CF3 〇 (PAG6-3)

V〇T (PAG7-1) (阙) .- f!

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs These photoacid generators are used based on the solid content of the composition, and can be used at 5% by weight, preferably 2% by weight. [2] (B) has at least one selected from the following general formula (la ') and general formula -28- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 520464 A7 ______B7_ 27 V. DESCRIPTION OF THE INVENTION A polymer (hereinafter referred to as a repeating unit represented by () (lb ')) and a repeating unit represented by the following general formula (II ·) and having a group (acid-decomposable group) decomposed by an acid action (hereinafter Referred to as "the resin of the present invention"). In the above general formula (la ·), the IΓ2 system each represents an independent hydrogen atom, a cyano group, a hydroxyl group, -C00H, -COOR'5, -CO-NH-R, -C0-NH-S02-R ' 6. Alkyl, alkoxy, or cyclic hydrocarbon groups which may have a substitution, or the following -Y group; wherein 1 ^ 5 is a substituted alkyl, cyclic hydrocarbon group, or the following -Y group; 6 represents an optionally substituted alkyl or cyclic hydrocarbon group; in the above-Y group, V21 to R'3 () each represents an independent hydrogen atom or an alkyl group which may have a substituent, and a and b represent 1 Or 2; X represents an oxygen atom, sulfur atom, -NH-, -NHS02, or -NHS02NH-; A represents a single bond or a divalent linking group. In formula (lb1), Z2 represents -0 or -N (ΙΓ3) ·; wherein, Γ3 represents a hydrogen atom, a hydroxyl group, or -0S02-R'4; RM represents an alkyl group, a halogenated alkyl group, or a cycloalkyl group Or camphor residues. The alkyl groups of R, R, 2, R, 4, R, 5, R, 6, R, 21 to R, and 30 are linear or branched alkyl groups having 1 to 10 carbon atoms. The preferred one is a linear or branched alkyl group having 1 to 6 carbon atoms, and the most preferred are methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, and 2-butane. And 3-butyl. Examples of the cyclic hydrocarbon group of R 1 i, R ′ 2, R ′ 5, R ′ 6 include cyclopropyl, cyclopentyl, cyclohexyl, arseno, 2-methyl-2-adamantyl, Original -29- The paper size of the table applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) " -------------- install --- (Please read the note on the back first Please fill in this page again for matters) · 丨 Line · Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumers' Cooperatives of the Ministry of Economic Affairs and the Intelligent Finance Covered Bureau 520464 A7 _B7___ 28 V. Description of the invention Base, tricyclodecyl, dicyclopentyl, protostilyl epoxy, lidyl, isodane, octyl, tetracycline and so on. Examples of the alkoxy groups of r, and r'2 include those having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, and butoxy. Examples of the halogenated alkyl group of IΓ4 include trifluoromethyl, nonafluorobutyl, pentafluorooctyl, and dichloromethyl. Examples of the above-mentioned R'4 ring group include cyclopentyl, cyclohexyl, cyclooctyl and the like. Examples of other substituents of the above-mentioned alkyl group, cyclic hydrocarbon group, and oxygen group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, a fluorenyl group, a cyano group, and a fluorenyl group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Examples of the alkoxy group include one having 4 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, and butoxy. Examples of the fluorenyl group include methyl fluorenyl and ethino. Base etc. For example, the divalent linking group of A in the general formulae (I a ') and (I b ·) is used alone or in combination of two or more kinds of alkylene groups, substituted alkylene groups, ether groups, thioether groups, carbonyl groups, and ester groups. , Sulfonamide, sulfonamide, urethane, and urea groups. Examples of the alkylene group and substituted alkylene group of A include a group represented by the following formula. -[C (Ra) (Rb)] r- (where Ra and Rb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, and the two may be the same or different. It is based on lower grades such as methyl, ethyl, propyl, isopropyl, butyl and so on. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the back (Please fill in this page again)

520464

V. Description of the invention (29) The better ones are transported from methyl, ethyl, propyl, and isopropyl. The substituents for the substituents are, for example, hydroxyl, halogen atom, and alkoxy. For example, the alkoxy is Those having a carbon number of 1 to 4 such as methoxy, ethoxy, propoxy, and butoxy. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. R is an integer of 1 to 10. ) Specific examples of the repeating unit represented by the above general formula (la ') are, for example, [1-1] to [1-65] below, but the present invention is not limited by these specific examples. (Please read the precautions on the back before filling this page)

The paper size printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 520464 A7 B7 V. Description of the invention (W) ^ CH- • CH 冲 0 = {r ° Pi] 0 = fr ° [1-2] 〇OH 〇1 OH C (CH3) 3 H3CH2C ~ C (CII3) 2 ^ CH- • CH ^ 0 = fr ° [i-3] r ° [1-4] s OH 〇1 OH 1 c (ch3) 3 ch2 1 OCH3 tCH- • CH ^ " " ^ CH- -CH " ^ 〇 = r Γ ° Μ 0 = fr ° 0 OH 〇1 OH | h3c-ch H3C -CH och2ch3 OCH2CH2CH2CH 3

tCH-: CH ^^ " ^ CH · -CH ^ 0 = f Γ0 a-τι 0 = f r ° i > 8] 〇 OH 〇 OH H3C-CH 〇CH2CH (CH3) 2

(Please read the notes on the back before filling this page) Binding: Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

r〇1 > 9] OH h3coh2c-c (ch3) 2 0 = f 0 1 C (CH3) 3 S02 CH, iQ〇 [M〇] -32- This paper standard is applicable to China National Standard (CNS) A4 (210 x 297 mm) 520464 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (w) 〇 = r 〇

r0 ①11] NH

[M2] 〇 〇t

r ° P-13] NH ^ CH-CH ^ 0 == ^ 〇d-14] C (CH3) 3 Ning 〇2 NH ch3 ^ CH-CH ^ 0 = ^ Γ0 [1-15] Lh3) 3 °, Qingchao H3C-CH OCH2CH3 S09 I-CH,

CH-CH x 〇 = f Γ0 [1-16] 〇, CH2 Qin 〇H 〇 = f r ° 0 0, C (CH3) 3 CH2CH2OCH2CH2COOH 〇 = f r ° 0 〇N ^ rTJ, ch2ch2conhso2ch3

Winter ^ CH-CH charge 〇 = {T = 〇 [1-19] 〇HN i (CH3) 3, ™ C〇〇H (Please read the precautions on the back before filling this page) [1-17] [1 -18]

tCH-CH only 〇 = (i = 〇α-2〇) 〇HN & H3) 3, called 〇H -33- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 520464 A7 B7 V. Description of Invention

VV yCH-CH 7 0 = ff = 〇 [1-21] 〇〇, I, ·, ch2ch2cn c (ch3) 3 " K 〇〇 < CH-C, 〇 [卜 胡 〇〇, i (CH3) 3 CH2CH2CO〇2Q V CH-CH 1 0 = ^ [1-22] 〇〇, I CH2CH2C〇OCH3 C (CH3) 3 V CH-CH 1 y = 0 [1-24] 〇, .〇0 == f 〇C (CH3) 3

〇V, CH-CH; 0 = (Υ = 〇 [I-25] 〇O, 〇IC (CH3) 3 h3c ^ h3c \ / CH-CH 〇 = fy = 〇〇〇. V CH-CH; [1 -26] ° = f 〇

[1-27] h3c-ch och2ch3 〇, .0

C (CH3) 3

[1-28] (Please read the precautions on the back before filling out this page) Packing. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

[1-29] C〇〇H \, CH-CH o = f ^ f = 〇 o 〇, [1-30] C (CH3) 3

[1-31]

[1-32] COOH This paper size applies to Chinese National Standard (CNS) A4 (210 x 297 mm) 520464 t: A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (wv yCH-CH 7 〇 = fy ^ 0 [1-33] OH OCH3 v .CH-CH J rl oc1o = f ^ 0 [i · 35] OH OCH2CH2CN CH-CH y 0 = f γ = 〇 [1-37] OH a

v yCH-CH J 0 = [OH

Sch2〇h _

,: CH-CH / rl0 = ^ γ = ο [卜 36] OH OCH2CH2COOH v yCH-HM 1〇 = <

OH

0 ^ 0

[! -38] -1 --- (Please read the notes on the back before filling this page) 0 = 1 ^ Γ ° [1-39] NH 0, S02 1 ^ ch3

0 0 v CH-CH '〇 = f Y = o 0 0, nc-h2ch2c

〇0 ^ CH-CH ^ 〇 = f Y = 〇 OH 〇

〇 = f Y = 〇 [1-40] OCH3

cr 0 、 CH-CH / r… [1-41] 0 = (Y = 〇 [⑷] och3 och2ch2cn [I-43] ^ CH-CH / 〇 = f γ = 0 OH 〇

[1-44] · 丨 line · -35. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 520464 A7 B7 V. Description of the invention (M

^ " CH-CH 0 = f r °

[1-49] ° Ύ T20 [1-50] 0 S C (CH3) 3 C (CH3) 3 0 = (f = 〇 [1-47]

OH OH o = f y = o 0 0 C (CH3) 3 C (CH3) 3

OH 0 = ^ ^ 1 = 0 [1-48] OH NHS02CH3 (Please read the notes on the back before filling this page) C (CH3) 3 C (CH3) 3 〇 = f Γ0 _ 0 0. ch2! OCHq ^ ch-ch " ^ 〇 = fr ° [1-52] 0 0, ch-ch3 och2ch3 〇 = (7 = 〇0 0 [1-53] C (CH3) 3 υ 0 = ^ F0 [1-54] 0 0 I l CH2 ch2 II OCH〇0 (¾ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 0 " ^ CH-CH ΐ ° ΐ Γ'0 hc-ch3 〒h -ch3 och2ch3 〇ch2ch3 —36 — Paper size Applicable to China National Standard (CNS) A4 (210 X 297 mm) 520464

F f · A7 B7 V. Description of the invention (w C (CH3) 3 〇 = (γ = οο ο i0 CH2OCH3 CI-56] [1-58] ^ CH-CH ^ 〇 = rr ° 0 1 s | i0 C ( CH3) 3 • CH 汴 r ° n 0 0 p 1 ch-ch3 alJ) och2ch3 [1-59] 〇 J30net

IS C (CH3) 3

[1-62] C (CH3) 3

[1-61] [1-63] C (CH3) 3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

° n r ° 0 0 I Ί C (CH3) 3 Π-64] ^ COOH

Γ _ ch2och3 • 37 · (Please read the notes on the back before filling this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (210 X zy / public reply) 520464 A7 B7-V. Description of the invention (36) Specific examples of the repeating unit shown by the above general formula (I b J are as follows [ Γ -1] ~ [I |-7], but the present invention is not limited by these specific examples. Ho c——c \\ o 1X- ti

CIC

NIH c o 1J 2- τ η o

CIC c— c r j 3- Ti I- >

H NIO o C——C \\ o t- c TJ 4- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Π3 NIC o 8 3 (Please read the notes on the back before filling this page)

This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 520464 A7 B7 V. Description of the invention (37) Γ, \\ ο

NIC ο 5 ore, T1 F3 CH—CH- ◦ 彡 C, / C > 〇 [Γ-6] o—so2 a cf3

Printed in the above general formula (II ·) by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, ^ 丨 factory ^^ each represents an independent hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent; Z series An atomic group containing two carbon atoms (CC) and forming an alicyclic structure with a substituent. • Examples of the halogen atom in R'n and R \ 2 include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. The alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and the most preferred is methyl group. Ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl. The substituents of the alkyl groups of the above R'M, IT12 are, for example, hydroxyl and halogen. -39- @ 张 标 Applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling (This page)

520464

7 7 A R V. Description of the invention (38) Meson, carboxyl, alkoxy, fluorenyl, cyano, fluorenyl and the like. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Examples of the alkoxy group include methoxy groups, ethoxy groups, propoxy groups, and butoxy groups having 1 to 4 carbon atoms. Examples of the fluorenyl group include methyl fluorenyl and ethyl fluorenyl. Base etc. The above-mentioned atomic group forming an alicyclic structure of Z is an atomic group of a repeating unit of an alicyclic hydrocarbon which may have a substituent in the resin. Among them, it is thought that the repeating unit of the alicyclic hydrocarbon which can form a bridge is formed. Atoms having a bridged alicyclic structure are preferred. The structure of the alicyclic hydrocarbon formed is, for example, the structure shown below. (Please read the precautions on the back before filling out this page) --- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs --- Order ---------- Line ---------- -* --- -40- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 520464 A7 B7 V. Description of the invention (Μ

A 6 6

\ 1/1 / ^, ⑵ ⑶ ⑷

% / 6 / (\ Λ- / ⑻ ⑼

; Install (Please read the precautions on the back before filling this page) 14)%

8 19) 20) / ι \ 2 22 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

---- Order --------- Line ---------------- 1 4 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Cent) 5. Description of invention (40)

Jy c6 (29) (28)

(36)

(30)

(31)

(35) (34) 6 0 (38) iD ⑤ Soil 7 (39)

(43) (Please read the notes on the back before filling this page) Binding. (40) (41) 丨 Line-cs > 1 ^ 17 (42)

(46) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (44) (45) (47) Preferred bridged alicyclic hydrocarbon architectures include, for example, (5), (6), (7) ), (.9), (10), (13), (14), (15), (23), (28), (36), (37), (42), (47). The alicyclic hydrocarbon structure may have a substituent.该 取 -42- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 520464 A7 B7 V. Description of the invention (41) For example, the general formula (11'-eight) or (11) {^ 13 ~ in '-8). Among the repeating units having the above-mentioned bridged alicyclic hydrocarbon group, the repeating unit represented by the above general formula (II'-A) or (IΓ-B) is more preferable. In the above general formula (II′-A) or (II · -B), only '13 ~ 1 ?, and 16 are each an independent hydrogen atom, halogen atom, cyano group, -COOH, -COOR'5 (R'5 series Represents an alkyl group which may have a substituent, a cyclic hydrocarbon group or the same -Y group as the general formula (1)), a group which is decomposed by an acid, -C (= 0) -XA-R_17, or may have a substituent Alkyl or cyclic hydrocarbon. n represents 0 or represents an oxygen atom, a sulfur atom, -NH_, -NHS02, or -NHSC ^ NH-. R'17 is -COOH, -COOR ,, -CN, hydroxyl, alkoxy which may have a substituent, -C0-NH-R, 6, -C0-NH-S02-R'6 (R, 5 , 1 ^, 6 are synonymous with the above) or -Y group of the above general formula (la). A is a single bond or a divalent linking group. The acid-decomposable group in the resin of the present invention also includes the above 4-(= 0) 7-AR \, -C (= 0) -XA-R'2, and also includes the substitution of Z in the general formula (II ·) base. The structure of the acid-decomposable group is represented by -C (= 0) -Xl-R0. (Wherein R0 includes, for example, tertiary alkyl groups such as 3-butyl and 3-fluorenyl groups, isobornyl, 1-ethoxyethyl, 1-butoxyethyl, and 1-isobutoxyethyl , Alkoxyethyl such as 1-epoxyethyl, alkoxymethyl such as 1-methoxymethyl, 1-ethoxyfluorenyl, 3-carbonylalkyl, tetrahydropyranyl, Tetrahydrofuranyl, trialkyl alkanoyl, 3-carbonylcyclohexyl ester, 2-methyl-2-adamantyl, methyllactone residue, 2- (r -butoxyloxy-43- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 Public Love 1 " (Please read the precautions on the back before filling this page).

= -0 '· -ϋ I 1 n ϋ I -ϋ I 1 n I 1 ϋ ft— nn · ϋ Li I Li I Lr Lr ϋ ϋ · 1 ϋ n ϋ ϋ ϋ · 1 I 52〇464 A7'- ----- B7_ V. Description of the invention (42) carbonyl) -2-propyl, etc., XI is synonymous with X above) -------------- install --- (please first Read the notes on the back and fill in this page) The halogen atoms of IT13 ~ R'16 are, for example, chlorine, bromine, fluorine, and iodine. The above-mentioned ^ 13 ~ 1 ^ '16 alkyl system is a linear or branched alkyl group having 1 to 10 carbon atoms, and the more preferable one is a linear or branched chain having 1 to 6 carbon atoms. The alkyl group is preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, or 3-butyl. Examples of the cyclic hydrocarbon group of R \ 3 to R'16 include a cyclic alkyl group, a bridged hydrocarbon, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an acrime alkyl group, a 2-methyl-2-aucamyl alkyl group, Orthospinyl, norbornyl, isobornyl, tricyclodecyl, dicyclopentyl, orthospinyl epoxy, cytyl, isocanyl, octyl, tetracyclododecyl and the like. At least two of the above IT 13 to 11 16 are bonded to form a ring, for example, a ring having 5 to 12 carbons such as cyclopentene, cyclohexene, cycloheptene, and cyclooctene. • Line · The alkoxy groups of 1 ^ 17 mentioned above include, for example, methoxy, ethoxy, propoxy, and butoxy groups having 1 to 4 carbon atoms. The substituents of the above-mentioned alkyl group, cyclic hydrocarbon group, and alkoxy group are, for example, a hydroxyl group, & , Cyano, fluorenyl and the like. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Examples of the alkoxy group include 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, and butoxy, and examples of the fluorenyl group include fluorenyl groups such as methyl fluorenyl and ethyl fluorenyl. Base etc. The above-mentioned divalent linking group of A is, for example, the same as the above-mentioned divalent linking group of A of the general formula Ua), and can be independently selected from a single bond, an alkylene group, a substituted alkylene group, -44- This paper size applies Chinese national standards (CNS) A4 specification (210 X 297 public love) " ~ 520464 V. Description of the invention (43, ether group, thioether group, carbonyl group, ester group, amidine group, sulfonamide group, urethane group , A group of urea groups, or a combination of two or more kinds of 23. The alkylene group and substituted alkylene group of A are, for example, the same as the divalent linking group of A of the general formula (I a '). The present invention The radical decomposed by the acid in the resin may contain at least one repeating unit represented by general formula (la '), the repeating unit represented by general formula (113') The superposition unit and the superposition unit of the following superposition unit of the copolymerization component: R, 13 ~ R'162 of the general formula (III · -A) or general formula (III, · B) are as described above Atoms of the alicyclic structure formed in the general formula (II) or substituents of the atomic group Z forming the bridged alicyclic structure Specific examples of the repeating unit represented by the general formula (II'-A) or the general formula (II'-B) are, for example, the following (II-1) to (11-66), but the present invention does not vary Specific examples are limited. The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy applies the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page)

520464 Α7 Β7 V. Description of the invention (#

0 0

0 0 [ΙΙ-2]

0 0

[ΙΙ-4] [II-3]

0 0 H CH (CH3) 〇CH2CH (CH3) 2 ο ο Η CH (CH3) 0CH2CH3

〇 [ΙΙ-6]

ο

[ΙΙ-8] ο ο 〇Y ^ j: (CH3) 3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [II-7]

Ο 0.

〇 xh2och2ch3

-46 _ (Please read the notes on the back before filling this page)

This paper size applies to China National Standard (CNS) A4 (210 X 2w mm) 520464 A7 B7

5. Description of the invention (4T

[π-ll] 0 0 NCH2CH2C C (CH3) 3

0 0 HOH2CH2C C (CH3) 3

[11-13] 0 0

[11-14] 0 0 hoh2ch2c ch2och2ch3 h3ch2coh2ch2c ch2och2ch3

[11-15]

[II-16] 0 0 0 0 hooch2ch2coh2ch2c ch2och2ch3

[11-17] ΝΉ0

NHO-equipment --- (Please read the precautions on the back before filling out this page) · -line · hooch2c Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy

[II-20] H3C-〇2S — HN-OC — H2CH2C C (CH3) 3 h3co2s ch2och2ch3 —47 — This paper size applies to China National Standard (CNS) A4 (210 X mm) 520464 A7 B7 V. Description of the invention (&Amp;

[11-22]

C (CH3) 3 [11-23]

(Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

-48 _ Loading -------- Order --------- Line ---------- It-- This paper size applies to China National Standard (CNS) A4 Specification (210 X 2y / mm) 520464 A7 B7 V. Description of the invention (ο

[II-31]

[11-32] 0 0 I

Η

[11-33]

η η [11-34]

0 [II-36] 0 0 (Please read the notes on the back before filling this page) 〇

ch2ch2oh Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

[II-39] = 〇 〇HN I CHoCOOH

-49-

This paper size applies to China National Standard (CNS) A4 (210x 297 mm) 520464 A7 B7 V. Description of the invention)

[11-41] 0 0 H C (CH3) 3

[11-42] 0〇

[II-43]

[ΙΙ-44] 0 0 (Please read the precautions on the back before filling this page) Install H CH2OCH2CH3

[II-45]

_ ΝΗ〇 Order: H CH (CH3) OCH2CH (CH3) 2 C (CH3) 3-On line · Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

〇〇 I

[II-47] = 〇

0〇 [II-48] 〇

〇 ch2〇ch2ch3 • 50 · ch2〇ch2ch3 〇 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 520464 A7 B7 V. Description of the invention (4?

[11-49]

[1I-50J

0 0 NCH2CH2C C (CH3) 3 0

[II-52] 0 0 HOH2CH2C C (CH3) 3 (Please read the precautions on the back before filling this page)

[II-53]

hoh2ch2c ch2och2ch3 h3ch2coh2ch2c ch2och2ch3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

[11-55] 〇〇 ho〇ch2c CH2OCH2CH3

〇〇 NCH2CH2C CH (CH3) OCH2CH3 [11-56] • 51. This paper size is applicable to China National Standard (CNS) A4 (210 x 297 mm) 520464 A7 ____ B7 V. Description of the invention (π)

[II-57] ΝΗΟ

H00C (H3C) HC CH (CH3) OCH2CH3 E.CO ^ HNOC ^ C C (CH3) 3

hoh2ch2cooch2c ch2och2ch3

[II-60] --Install—— (Please read the precautions on the back before filling this page)

[11-61]

[11-62] (T CH2OCH2CH3 .-I line · Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economy

-52- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 520464 A7 B7 V. Description of the invention (d

[11-66]

[11-67] (Please read the precautions on the back before filling in this page), 0 0 8 A w A A / 0 0 CH (CH3) OCH2CH (CH3) 2)) CH2OCH2CH3

[11-68]

[11-69] car ◦〇 i ch2och3

0 0 1 CH (CH3) OCH2CH3 -_line · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

H〇〇C

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 520464 A7 B7 V. Description of the invention (η

[II-71] 0 0 I Η

[11-72] 0 0 I

Η

[11-73] [II-75] 〇〇y

C

[11-74]

ch2ch2oh .0 0

Pd Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

[11-77] 0 = ^ ^ = 0 Ό〇

[11-78], 0 0 〇 = < > = 〇

Pd ch2ch2cn

HO

CHoCH.OH -54- (Please read the precautions on the back before filling this page)

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 520464 A7 B7 V. Description of invention (shirt

[11-79]

[II-80j ch2cooh

0 C (CH3) 3 CII-81]

, 〇ΗΝ

[11-83] I CHoOCHoCH,

0 I

[II-84]

[11-86] CH (CH3) OCH2CH3 CH (CH3) OCH2CH (CH3) 2 r) Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs

[11-88] 〇 ·

[11-89] 0 -55 · (Please read the precautions on the back before filling this page)

This paper size applies to China National Standard (CNS) A4 specification (210 X 29 / β centimeter) 520464 A7 B7 V. Description of invention (discussion)

[11-97] (Please read the precautions on the back before filling this page)-

[II-98] 〇

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

[II-100] [11-102] 〇, ch2ch2och2ch3 〇, ch2co〇h • 56 · This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ---- order ----- ---- Line ------------ ί -1. -J n I n II ϋ n-520464 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

[ΙΙ-103]

HN N

[II-104]

, CH2CH2OCH2CH2OH

HN.

[11-105], CH (CH3) C0C

0 〇

[11-108] [11-110] HN

CH2COOCH2CH2CN

HN. N

[11-112] ch2cooh

〇 HN, [11-106]

[11-109]

XH (CH3) COO

HN · CH2COOCH2CH2OCH2CH3 • 57- -a0 [II-111]

XH2COOCH2CH2OH (Please read the precautions on the back before filling this page)

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 520464 A7 B7 V. Description of the invention (汴

CH2OCH2CH3

[II-118]

〇 [II-120]

〇 〇

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

〇 [II-124] 〇 (Please read the notes on the back before filling in this page)

Each paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 520464 A7 B7 V. Description of the invention)

[11-130]

〇CH〇CH〇CN

so2ch3

(Please read the precautions on the back before filling out this page) Installation 丨 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

〇 I

[II-133]

ch2ch2〇ch2ch3

〇CHoCOOH -59- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 520464 A7 B7 V. Description of the invention (w

〇 [11-135]

ch2ch2och2ch2oh ch2cooh

CH (CH3) COOH

[11-141] HN

[II-142] 0 CH2C00- < ^^

[H-139] --Install --- (Please read the precautions on the back before filling in this page) CH (CH3) C00- 0 〇 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

[11-143] HN

[11-144] HN

CH2COOCH2CH2CN

CH (CH3) COOCH2CH2OH -go- This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) 520464 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

ΗΝ [11-145]

0 ΗΝ I

CHoCOOCHXHoOH

[11-147]

CN CH2COOCH2CH2〇CH2CH3 [11-149] [11-148]

Cl

[11-149] F C CN

[II-150] HO

[II-151] CONH〇-· 装 --- (Please read the precautions on the back before filling this page) [11-152] h3c conh2

[11-155] [11-153] [11-154] C0NHC (CH3) 2CH2S03H 〇coch3

[11-157] Order: Line · [II-156]

[11-160] • 61 · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Cl CONH, 520464 A7 B7 V. Description of the invention (60)

[11-162]

C0NHC (CH3) 2CH2S03II

[II-163] OCOCH,

[II-165]

[11-166] The resin of the present invention contains one of several types of general units (la J and / or general formula (I b ')), and any of the general units (IΓ) (including general units In general, it is necessary to adjust the dry etching resistance or standard imaging solution suitability, substrate adhesion, outer shape of the barrier, and the barrier in addition to the repeating units shown in formula (IΓ-Α) and general formula (ΙΙ · -Β)). For the purpose of resolution, heat resistance, sensitivity, etc., the copolymer may include multiple units of various monomers. Preferred copolymer components include, for example, the weights shown by the following general formula (IV ') (V'). ------------- Install—— (Please read the precautions on the back before filling this page).

〇Z 〇

[V,] 〇 'z 〇 (wherein Z represents a hydrogen atom, -NH-, N (ΙΓ50)-, -N (-0S02IT5 ())-, and R'5Q is the same (substituted) alkane as above Base-62- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 520464 A7 _B7_ V. Description of the invention (61) (Substituted) cyclic hydrocarbon group The above general formula (IV '), (V Specific examples of the repeating unit shown in ') include the following (IV, 9) to (IV'16), (V, 9) to (V'-16), but the present invention is not limited to these specific examples. (Please read the precautions on the back before filling this page) --Installation • Thread. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. This paper is printed in accordance with China National Standard (CNS) A4 (210 X 297 mm) 520464 A7 B7 V. Description of Invention)

Η 〇so2ch3

[IVM5] 〇

0S02-CF2 (CF2) 6CF3 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

〇 ’ο ο

[V, -11] Η -64- Wood paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) oso2ch3 i pack --------- Order -------- -Line ------------ I 4 ϋ m 1 I ϋ II. 520464 A7 B7 V. Description of the invention (63,

[V, -14] -〇

0S02-CF2 (CF2) 6CF3 (Please read the precautions on the back before filling out this page) The Intellectual Property Bureau of the Ministry of Economic Affairs has printed the resin of the present invention within the scope of the effect of the present invention. The monomers are copolymerized as repeating units constituting the resin, but are not limited by the monomers described below. This makes it possible to fine-tune the properties required for the above resins, in particular (1) the resolvability to the coating solvent, (2) the film forming properties (glass transition temperature), (3) the alkali developability, and (4) the film edges (Hydrophilicity, alkali-soluble group selection), (5) adhesion to the substrate of the unexposed portion, and (6) dry etching resistance. The comonomer includes, for example, acrylates, methacrylates, ammonium acrylates, ammonium methacrylates, allyl compounds, vinyl ethers, vinyl esters, and the like, each having a property selected from addition polymerization Unsaturated compounds. -65--丨 install -------- order --------- line ----- · B ·· — —ϋ I m% wi 1 · mmws —Bi ϋ · ϋ ιϋ纸张 ··· This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 52〇464 A7 B7 $, Description of Invention (64) Specifically, for example, acrylic esters such as alkyl acrylate (alkyl The carbon number is preferably from 1 to 10) esters (such as methyl acrylate, ethyl acrylate, propyl acrylate, pentyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylic acid-number 3- Octyl ester, ethyl chloride acrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxybenzyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, Benzyl acrylate, methoxybenzyl acrylate, acetic acid propionate, tetrahydropropionyl propionate); methacrylic esters such as alkyl methacrylate (Preferred) (such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, methyl methacrylate, methyl propyl Hexyl acid, cyclohexyl methacrylate, benzyl methacrylate, benzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate , 5-hydroxybenzyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, methacrylate Esters, tetrahydrofluorenyl methacrylate, etc.); acrylamides such as acrylamide, N-alkyl acrylamide (alkyl is 1 to 10 carbon atoms, such as methyl, ethyl, propyl, Butyl, 3-butyl, heptyl, octyl, cyclohexyl, hydroxyethyl, etc.), N, N-dialkylpropenamide (alkyl is 1 to 10 carbons, such as methyl, ethyl Group, butyl, isobutyl, ethylhexyl, cyclohexyl, etc.), N-hydroxyethyl-N-methacrylamide, N-2-vinylfluorenamineethyl-N-ethenylpropenefluorene Amines, etc .; methacrylamide, for example, methacrylamine, N-alkylmethylpropane-66- This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) (please first Note Complete this page and then read it back) Ministry of Economic Affairs Intellectual Property Office fi printing staff of consumer cooperation

520464 A7 B7 65 V. Description of the invention () melamine (alkyl is 1-10 carbon, such as methyl, ethyl, 3-butyl, ethylhexyl, hydroxyethyl, cyclohexyl, etc.), N, N-dialkylmethacrylamide (alkyl is ethyl, propyl, butyl, etc.), N-hydroxyethyl-N-methylmethacrylamine, etc .; Allyl compounds are, for example, Allyl esters (such as allyl acetate, allyl hexanoate, allyl hexanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, acetamidine Allyl acetate, allyl lactate, etc.), allyloxyethanol, etc .; Examples of vinyl ethers are alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, Methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chlorinated ethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyl Ethyl vinyl ether, diethylene glycol vinyl ether, dimethylamino ethyl vinyl ether, diethyl amino ethyl vinyl ether, butyl amino ethyl vinyl ether, benzyl vinyl ether, tetrahydro Fluorenyl vinyl ether, etc.); vinyl esters include, for example, vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl citrate, vinyl caproate, and chlorinated acetic acid Vinyl Ester, Vinyl Dichloride, Vinyl Methoxy Acetate, Vinyl Butoxy Acetate, Ethyl Vinyl Acetate, Vinyl Lactate, Vinyl / 3-Phenyl Butyrate, Vinyl Cyclohexyl Carboxylate Esters, etc .; dialkyl itaconates (such as dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); acrylic acid, methacrylic acid, citric acid, itaconic acid, acrylonitrile , Methacrylonitrile and so on. In the resin of the present invention, the general formula (la ') and / or the general formula (lb') are -67- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) installed --- (Please First read the note on the back? Matters and then fill out this page) · Line -1 · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 66 520464 V. • Description of the invention (indicating repeating units and general formula (II)) (including The content of the repeating unit shown in the general formula (II, -A) and the general formula (IΓ-B)) is the dry etching resistance, sensitivity, pattern crack prevention, substrate adhesion, and resistance of the desired resist. The resolution, heat resistance, etc. of necessary elements of the general resistance body are appropriately set. In general, the unit of the resin of the present invention is represented by the general formula (la ') and / or the general formula (lb'). And the content of the repeating unit shown in the general formula (II ′) is 25 mol% or more, preferably 30 mol% or more, and more preferably 35 mol% or more in the total repeating unit of the resin. In addition, from the above-mentioned preferred comonomers in the resin of the present invention The content of the raw repeated unit (general formula (IV ·) or general formula (V,)) in the resin is appropriately set according to the desired barrier properties, but in general, the general formula (la ') and / Or the total number of repeating units represented by the general formula (lb,) and the repeating units represented by the general formula (II ') is preferably 99 mol% or less, and more preferably 90 mol % Or less, the best is 80 mole% or less. In addition, the content of the resin in the above-mentioned repeating unit based on the monomer of the copolymerization component is also appropriately set according to the desired barrier properties, but it is generally It is preferable that the total molar number of the repeating unit represented by the general formula (la,) and / or the general formula (lb,) and the total repeating unit represented by the general formula (11 ′) is 99 mol% or less. More preferably, it is 90 mol% or less, and most preferably, 80 mol% or less. When the coating unit amount based on the monomer of the copolymerization component is more than 99 mol%, the present invention cannot be obtained sufficiently. The effect is not to be desired. -68- The size of this paper is + ¾¾ (CNS) A4 size⑵0 X 297mm) 520464 A7 ^ ------- B7__ V. Explanation of the invention (67) Moreover, the base decomposed by the acid action in the resin of the present invention contains the general formula (la ·) and / or the general formula (lb '). Any of the repeating units shown in the formula, the repeating units shown in the general formula (IΓ), and the repeating units based on the monomer of the copolymerization component may be used. For all repeating units, it is 8 to 60 mol%, preferably 10 to 55 mol%, and more preferably 12 to 50 mol%. The resin of the present invention can copolymerize the monomer and maleic anhydride in the repeating unit represented by the general formula (II ') with the monomer of the copolymerization component when a copolymerization component is used, and copolymerize in the presence of a polymerization catalyst. Polymerize, repeat the unit of maleic anhydride of the obtained copolymer under basic or acidic conditions, ring-open with an alcohol, or hydrolyze it, and change the carboxylic acid moiety formed afterwards with the desired substituent Methods were synthesized. The weight average molecular weight of the resin of the present invention is preferably 1,000 to 200,000 in terms of polystyrene conversion by the GPC method. If the weight average molecular weight is less than 1,000, it is not desirable because heat resistance or dry etching resistance is deteriorated. If it is more than 200,000, the film forming property is not good due to poor developability and extremely high viscosity, resulting in undesired results. In the positive-type photoresist composition for far-ultraviolet exposure of the present invention, the compounding amount of the entire resin composition of the present invention is preferably 40 to 99.99% by weight, and more preferably 50 to the total solid content of the resist. 99.97% by weight. [3] Fluorine-based and / or silicon-based surfactant The first photoresist composition of the present invention preferably contains a fluorine-based and / or silicon-based surfactant. The positive photoresist composition of the second invention requires a fluorine-based or silicon-based surfactant. -69- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Packing-(Please read the precautions on the back before filling this page) · • Line. Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 520464 Α7 Β7 v 68 V. Description of the invention () The fluorine-based and / or surfactant is at least one fluorine-based surfactant, silicon-based surfactant, and fluorine-containing Surfactant for both atoms and silicon atoms. The positive photoresist composition of the present invention contains the above-mentioned acid-decomposable resin and the above-mentioned surfactant, and when using an exposure light source of 250 nm or less, especially 220 nm or less, sensitivity, resolution, substrate adhesion, and dry etching resistance can be obtained. It is excellent in performance, and rarely has a development defect and a residue blocking pattern. Such surfactants include, for example, JP 62-36663, JP 61-226746, JP 61-226745, JP 62-170950, JP 63-34540, and JP 7 The surfactants described in -230165, Japanese Patent Application Laid-Open No. 8-62834, Japanese Patent Application Laid-Open No. 9-54432, Japanese Patent Application Laid-Open No. 9-5988 can also be used directly as described below. Commercially available surfactants can be used, for example, Gefton Department (Transliteration) EF301, EF303 (Sin Akita Kasei Co., Ltd.), Floraton (Transliteration) FC430, 431 (Sumitomo Shrimiya (Co.)) ), Merkafak (transliteration) F171, F173, F176, F189, F08 (made by Dainippon Ink Co., Ltd.), Safran (transliteration) S-382, SC101, 102, 103, 104, 105, 106 ( Asahi Glass Co., Ltd.) and other fluorine-based surfactants or silicon-based surfactants. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant. The compounding amount of the above-mentioned surfactant is based on the solid content in the composition of the present invention, and is usually 0.001% by weight to 2% by weight, preferably 0.001% by weight to 1% by weight. -70- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) -------------- Loading --- (Please read the precautions on the back before filling (This page).-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 520464 A7 B7 69 V. Description of the invention () These surfactants can be used alone or in combination of two or more. The positive-type photoresist composition of the present invention may use a surfactant other than the above-mentioned (C) fluorine-based and silicon-based surfactants. Specific examples of other surfactants that can be used include, for example, polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide hexadecyl ether, and polyethylene oxide oleate. Ethylene oxide alkyl ethers, polyethylene oxide octyl phenol ether, polyethylene oxide nonyl phenol ether and other polyethylene oxide alkyl aromatic ethers, polyethylene oxide and polypropylene oxide Block copolymers, sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, sorbitol Sorbitol fatty acid esters such as tristearate, polyethylene oxide sorbitol monolaurate, polyethylene oxide sorbitol monopalmitate, polyethylene oxide sorbitol monostearate Non-ionic surfactants such as polyethylene oxide sorbitol fatty acid esters, such as esters, polyethylene oxide sorbitol trioleate, polyethylene oxide sorbitol tristearate, and the like. The compounding amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight, with respect to 100 parts by weight of the solid content in the composition of the present invention. These surfactants can be added alone or in combination. [4] Organic basic compound The preferred organic basic compound used in the present invention is a compound which is more basic than phenol. The nitrogen-containing basic compound containing a structure shown in the following (A) to (E) is preferred. By using a nitrogen-containing basic compound, the performance change is small even after exposure to heating. -71- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -1 --- (Please read the precautions on the back before filling this page) .- • Line 丨 · 520464 A7 B7 5 , Description of invention (70 R251

R 250. Gan. R252 (Among them, R25G, R251 and R252, alkyl groups having 1 to 6 carbon atoms, carbon atoms 胺 same or different carbon atoms having 1 to 6 amino alkyl groups, and carbon groups having 1 to 6 carbon atoms Or substituted or unsubstituted aryl group having 6 to 2G carbon atoms, and R251 and R252 may be bonded to each other to form a ring) -N-: N- (B) CN ^ c-- (C) C-N-- (D) R254 R255 C—N—C-—R256 -_Shang— (Please read the note on the back? Matters before filling out this page} Order R: 253 (E) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ( Among them, R 2 5 3, R 2 5 4, R 2 5 5 and R 256 may be the same or different alkyl groups having 1 to 6 carbon atoms.) Preferred examples include substituted or unsubstituted veins, substituted or Unsubstituted aminopyridines, substituted or unsubstituted aminoalkylpyridines, substituted or unsubstituted aminopyrrolidines, substituted or unsubstituted-72- This paper applies Chinese national standards ( CNS) A4 size (210 X 297 public love) 520464

V. Description of the invention: Imidazole, substituted or unsubstituted pyrazole, substituted or unsubstituted ftazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted hey, substituted or unsubstituted Substituted imidazolines, substituted or unsubstituted pyrazolines, substituted or unsubstituted piperidines, substituted or unsubstituted morpholines, substituted or unsubstituted aminomorpholines, and the like. Preferred substituents are amine, aminoalkyl, alkylamino, aminearyl, arylamino, alkyl, alkoxy, fluorenyl, fluorenyl, aryl, aryloxy, nitrate More preferred compounds are, for example, vein, -dimethyl vein, 1, 13, tetramethyl vein, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2 -Dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amine 4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-amino Pyrrolidine, piperazine, N- (2-aminoethyl) piperazine N · (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-pyranylpiperidine, 2-iminopyrimidine, 1- (2-Aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tripyrazole, pyrazine, 2- ( Aminomethyl) 5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-amino group Phthaloline, N- (2-aminoethyl) morpholine, 1,5-diazobicyclo [4,3,0] non-5-ether, 1,8-one diazo ring [5,4, 0] Undec-7-one, 2,4,5-triphenylimidazole, tri (n-butyl) amine, tri (n-octyl) amine, N-benzyldiethanolamine, N-hydroxyethyl piperidine Pyridine, 2,6-diisopropylaniline, N-cyclohexyl-N1-morpholineethylthiourea-73- @ 目 家 鲜 （CNS) A4 Specification (210 X 297 mm)-Packing-( Please read the notes on the back before filling this page) ί Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employee Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employee Cooperatives of the Intellectual Property Bureau of the Ministry of Economics 520464 A7 B7 72 Butylmorpholine is not limited by these. More preferred are 1,5-diazobicyclo [4,3,0] non-5-one, 1,8-diazobicyclo [5,4,0] undec-7-one, 2 , 4,5-triphenylimidazole, tri (n-butyl) amine, tri (n-octyl) amine, N-benzyldiethanolamine, N-hydroxyethylpiperidine, 2,6-diisopropyl Aniline, N-cyclohexyl-N'-morpholine ethylthiourea, N-hydroxyethylmorpholine. These nitrogen-containing basic compounds can be used alone or in combination of two or more. Use of nitrogen-containing basic compounds The amount is generally 0.001 to 10% by weight, and preferably 0.01 to 5% by weight, based on the total solid content of the photosensitive resin composition. If it is less than 0.011% by weight, the above-mentioned addition effect of the nitrogen-containing basic compound cannot be obtained. If it is more than 10% by weight, the sensitivity tends to decrease or the developability of the non-exposed portion tends to deteriorate. [5] Other additives, preparation method of positive photoresist composition, method of use, etc. The positive photoresist composition of the present invention may be added with an acid decomposable solvent to prevent the compound. This can improve the contrast and resolution, and make the pattern rectangular. Examples of the acid-decomposable dissolution-preventing compounds include compounds that contain acid-decomposable groups, which are decomposed by the action of an acid, and which increase the solubility in an alkali developing solution, in order to reduce the light absorption of the resist film exposure. The aromatic group-containing compound is more preferably a compound having a monocyclic or polycyclic cyclic hydrocarbon structure. This can improve dry etching resistance. Monocyclic or polycyclic alicyclic hydrocarbon structures include monocyclic cycloalkane structures, adamantane structures, protospinane structures, and nested structures. The acid-decomposable dissolution preventing compound contains an acid-decomposable group which is preferably a group protected from carboxylic acid acetic acid. Examples of the acid-decomposable group include tertiary alkyl esters such as 3-butyl ester and 3-fluorenyl ester. Base, -74-i paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) '------------- installation -------- order- ------- Line (Please read the note on the back? Matters before filling out this page) 520464 A7 B7 73 V. Description of the invention () 1-alkoxyethyl, 2-tetrahydropyranyl and other chains Shaped or cyclic acetal ester group. Preferred is a tertiary alkyl ester group. The amount of the acid-decomposable dissolution preventing compound in the positive-type photoresist composition of the present invention is usually 1 to 30% by weight, preferably 5 to 20% by weight based on the solid content of the composition. The positive photoresist composition of the present invention may contain a dye, a plasticizer, a sensitizer, and a compound that promotes solubility in a developing solution, etc., as necessary. The positive-type barrier composition of the present invention is one in which the above-mentioned components are dissolved in a solvent and coated on a carrier. The solvents used herein are ethyl dichloride, cyclohexyl ether, cyclopentanone, 2-heptanone, 7-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methoxy Methyl propionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylmethylene maple, N-methylpyrrolidone Tetrahydrofuran and the like are preferred, and these can be used alone or in combination. Preferred solvents among the above are, for example, 2-heptanone, r-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and methyl lactate , Ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, N-methylpyrrolidone, tetrahydrofuran. The positive resist composition of the present invention is coated on a substrate to form a thin film, and the film thickness of the coating film is preferably 0.2 to 1.2 // m. In the present invention, Vision-75- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the back? Matters before filling out this page) ----------line

Printed by Employee Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs A7

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 520464 V. Description of Invention (74) A commercially available inorganic or organic anti-reflection film can be used as required. As the anti-reflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, α-silicon dioxide, or an organic film type made of a light absorbing agent and a polymer material can be used. The former must use equipment such as a vacuum evaporation apparatus, a CVD apparatus, and a sputtering apparatus for film formation. The organic anti-reflection film includes, for example, a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin, an alkali-soluble resin, and a light-absorbing agent described in Japanese Patent No. 7-6961 1, or Malay described in US Patent No. 5,294,680. Reactant of an acid anhydride copolymer and a diamine-type light absorbing agent, which contains a resin binder and a methylolmelamine-based thermal cross-linking agent described in Japanese Patent Application Laid-Open No. 6-1 1 8631, described in Japanese Patent Application Laid-open No. 6-1 18656 Acrylic resin-type antireflection film having a carboxylic acid group, an epoxy group, and a light-absorbing group in the same molecule, and is made of methylolmelamine and benzophenone-based light absorbing agent described in JP-A-8-87115. For example, a low molecular weight light absorbing agent is added to the polyethylene glycol resin described in Japanese Patent Application Laid-Open No. 8-1 79509. In addition, as the organic anti-reflection film, it is also possible to use DUV30 series or DUV-40 series manufactured by New Vasant Anthony Co., Ltd., AC-2, AC-3, etc. manufactured by Western Lightning Co., Ltd. The above-mentioned body-blocking fluid is placed on a substrate (such as a silicon / silicon dioxide coating) used in manufacturing a precision integrated circuit element (as required, on a substrate provided with the above-mentioned antireflection film) by a spinner, a roller, etc. After being coated by an appropriate coating method, exposure is performed through a predetermined photomask, baking is performed, and a good resist pattern is produced by development. Here, the exposure light is preferably light having a wavelength of 150 nm to 250 nm. Specifically, for example, there are KrF excimers -76- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back? Matters before filling out this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 520464 A7 ____B7_____ V. Description of the invention () Laser (248nm), KrF excimer laser (193nm), F2 excimer laser (157nm), X-ray, electron beam, etc. As the developing solution, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methylsilicate, and ammonium water, primary amines such as ethylamine and n-propylamine, and diethylamine and di-n-propylamine can be used. Secondary amines, tertiary amines such as diethylamine, methyldiethylamine, alcohol amines such as dimethylethanolamine, triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, pyrrole Alkaline aqueous solutions such as cyclic amines such as piperidine. In addition, appropriate amounts of alcohols and surfactants can be added to the alkaline aqueous solution. [Examples] The following describes the first invention of the present invention more specifically with reference to the following examples, but the present invention is not limited to the following examples. [Synthesis of Photoacid Generator of Component (A)] The compounds of the general formula (I) '(II) include, for example, an aryl Grignard reagent such as an aryl magnesium bromide and a substituted or unsubstituted benzene Methanesulfonic acid reaction, a method for exchanging the obtained triarylsulfonium salt halide with the corresponding sulfonate, or using a substituted or unsubstituted phenylenesulfonate and the corresponding aromatic compound using methanesulfonic acid / pentaoxine Or a method of condensing and salt exchange using an acid catalyst such as aluminum chloride, and a method of condensing and salt exchange using a diaryl iron iodide salt and a diaryl sulfonate using a catalyst such as ketone acetate. The sulfonic acid or sulfonate used in the above-mentioned base exchange can be obtained by hydrolyzing or the like of a commercially available sulfonic acid halide. For the synthesis of the photoacid generator in the following component (A), for example, the following 3 cases -77- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Packing --- (please first Read the Zhuyin on the back? Matters need to fill in this page) Line · 520464 A7

V. Description of the invention (76) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the other photoacid generators used in Table 2 below are synthesized in the same way or in the general method 1 described above. Synthesis of 3-butylphenyl) sulfoperfluoro-n-butanesulfonate (1_2) -Butylphenyl) iodonium salt Perfluoro-n-butane sulfonate (20 mmol) and benzoate ether (4 mmol) were stirred under a stream of nitrogen at 130 ° C for 4 hours. The reaction solution was allowed to cool, and 100 ml of methanol was added thereto to remove precipitates. The target filtrate was concentrated, and 200 ml of ether was added to precipitate a powder, which was filtered, washed with ether, and dried to obtain 5. lg target. Synthesis Example 2 < Synthesis of tris (3-butylphenyl) sulfoperfluoro-n-octane sulfonate (1-4) > Using the same method as Synthesis Example 1, -Butylphenyl) Iodophosphonium salt perfluoro-n-octane sulfonate was substituted for the bis (3-butylphenyl) ferric iodonium salt perfluoro-n-butane sulfonate to obtain 6.2 g of the desired product. Synthesis Example 3 < Synthesis of bis (p-chlorophenyl) phenylsulfoperfluoro-n-butanesulfonate (1-6) > 1009 bis (p-chlorophenyl) sulfonate was dissolved in In 800 ml of benzene, 295 g of aluminum chloride was added thereto and refluxed for 24 hours. The reaction solution was slowly poured into 2 L of water, 400 ml of concentrated hydrochloric acid was added thereto, and the mixture was heated at 70 ° C for 10 minutes. This aqueous solution was washed with 500 ml of ethyl acetate to obtain a bis (p-chlorophenyl) phenylphosphonium salt. Add 3.8g of trifluoromethanesulfonate-78 to 150ml of this aqueous solution. This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm)-Install i I (Please read the precautions on the back before filling this page ). 丨 line. 520464 A7 B7 1. Description of the invention (Aqueous solution of sodium 77. It was extracted with ethyl acetate, and the organic phase was washed with distilled water, dried, and concentrated to obtain 4.3 g of the target. [( B) Synthesis of component resins (1) to (8)] Synthesis Example 4 A tetracyclic ring obtained by reacting a 3-carbon-based 1,1-monomethylbutanol propionate with cyclopentadiene A mixture of dodecene derivative (1 -1) and mol such as maleic anhydride was dissolved in tetrahydrofuran to prepare a 50% solids solution. The solution was added to a 3-necked flask under a nitrogen stream at 60 ° C. Heating. At a stable reaction temperature, add 5 mol% of free radical starter V-60 manufactured by Wako Pure Chemical Industries, Ltd. to start the reaction. After heating for 6 hours, the reaction mixture was diluted twice with tetrahydrofuran, and a large amount of hexane was added. White powder is precipitated. The precipitated powder is filtered out and dried to obtain the target resin (1)

ch3 ch. CH3 COG—C——CH2—C—CH. , ^ II, 〇 (1-1) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. When the resin (1) was measured by GPC molecular weight analysis, it was 6800 (weight average) in terms of polystyrene. Moreover, the molar ratio of the resin (1) tetracyclododecene repeating structural unit to the maleic anhydride repeating unit by the MMR spectrum is 50/50. Resins (2) to (10) were synthesized in the same manner as in Synthesis Example 4. The structures of the synthetic resins (1) to (10) are as follows. -79- The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

520464 A7 B7 V. Description of the invention (CH,

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7 7 A B 81 V. Description of the invention () Table 1 shows the molar ratios and weight average molecular weights of the respective repeating units of the above resins (1) to (10). Table 1 -------------- Packing --- (Please read the notes on the back before filling this page). Delete the mole ratio maleic anhydride Mole ratio IH of maleate [Mean average molecular Li ^ 丨 Right Left 1 Right (1) 50 '-50 6800 ⑵ 50' 50 6500 (3) 34 16 50 5700 (4) 36 14 50 6700 (5) 50 28 | 22 6600 (6) 38 ~ [Ϊ2 50 5900 (7) 50 50 9200 (8) 50 ~ '50 11000 Solvent blocker, line. In an oven-dried Schnenke tube replaced with argon Medium charge (drying in a vacuum tube at 60 ° C overnight) 3-butyl cholic acid (2.07g, 4.457 mmol), N · methylmorpholine (distilled from CaH2) (1.1 mL, 10 mmol) and methyl chloride (8 mL). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to cool the mixture to 0t :, and then slowly add dichloropentyl only (0.55 2g, 4.324 millimoles, 97 mol%) using a gas-tight injector. ). After the addition was completed, the salt began to precipitate. The obtained slurry was stirred 'and warmed to room temperature in 30 minutes, and heated at 40 ° C for 30 minutes. Then the mixture was poured into a separatory funnel containing methyl chloride (40 ml) and water (40 ml). The organic layer was washed 4 times with a dilute aqueous ammonium acetate solution and then concentrated to obtain a solid. This solid was freeze-dried from dioxane to obtain a powder. -83- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 x 297 mm) 520464 A7 B7 82 V. Description of the invention (Disperse the powder in water (100ml), stir for 1 hour. Filter and make the powder It was recovered and dried in vacuum. The yield was 1.5 g (yield 64%). When the method was repeated using tetrahydrofuran (THF), the yield was 1.7 g (yield 74%). The obtained oligomer The structure is shown below. This oligomer is used as the dissolution inhibitor A. (Please read the precautions on the back before filling out this page) Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economy -84-

This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 520464 V. Description of the invention (N) Printing of clothing by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 3 〇

(Please read the precautions on the back before filling this page) The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) —85— 520464 A7 ____ B7 84 V. Description of the invention () Butylcholate-terminated oligomers (3-butylcholate-co-glutarate) (wherein tBu is 3-butyl, Y is hydrogen, or any of Other units in the structure defined by the letter M or 1) The number of units M in the molecule is approximately 5-20. The condensation reaction described above can produce any oxo group on a polycyclic compound. Therefore, the above structures are those who can help explain the reaction products and are not the actual structures of the obtained products. [1 to 1 of Example 1 and 1 to 6 of Comparative Example 1] (1 to 15 of Comparative Example 1 and 1 to 6 of Comparative Example 1) (Orthophotoresist composition) Various types shown in Table 2 The ingredients were used in the amounts shown below. Resin shown in Table 2 synthesized in the above synthesis example: 2.0 g, photoacid generator: 0.02 g, organic basic compound (amine): 0.001 g, surfactant: 0.004 g, solid content of the composition of each example After dissolving it in propylene glycol monoethyl ether acetate at a concentration of 14% by weight, it was filtered with a 0.1 / m micro filter to prepare positive photoresist of Examples 1 to 2 and Comparative Examples 1 to 6. Composition solution. In addition, when the dissolution inhibitor (dissolution inhibitor A or 3-butyl cholic acid) was added, the amount added was 0.5 g. The photoacid generator, organic basic compound (amine), and surfactant are used as follows. Photoacid generator-8 6- The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) ----------------- Packing-- (please first Read the notes on the back and fill in this page) Order: -Line-Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by 520464 A7 B7 85 V. Description of Invention () Phenylphosphonium salt perfluoro-n-butane sulfonate PAG-B: bis (4-th 3-butylphenyl) iron iodonium salt trifluoromethane sulfonate PAG-C: bis (4-th 3-butyl Phenyl) iron iodide nonafluoron-butane sulfonate PAG-D: 4-methoxy-1-naphthyl tetraargonylsulfanyl nonafluoron-butane sulfonate PAG-E: N-trifluoromethane Ammonium salt succinimide (1): 1,5-diazobicyclo [4 · 3 · 0] -5 -nonan (2) · 2,4,5-triphenylimidazoline (3 ): Tri-n-butylamine (4): N-hydroxyethylpiperidine surfactant is W-1: Mekafak (transliteration) F176 (made by Dainippon Ink Co., Ltd.) (fluorine) W -2: Mekafak R08 (manufactured by Dainippon Ink Co., Ltd.) (fluorine and polysiloxanes) W-3: polysiloxane polymer KP-341 (by Shin-Etsu Chemical Industry Co., Ltd.) W-4: Dunroy Rolu S-366 (Dunroy Chemical Co., Ltd.) (Silicon) (Evaluation test) The obtained positive photoresist composition solution was spin-coated The cover was coated on a sand wafer and dried at 1 40 ° C for 90 seconds to form a positive photoresist film of about 0.5 // m, and was exposed thereon with an ArF excimer laser (193nm). The heat treatment after exposure was performed at 140 ° C for 90 seconds, developed with a 2.38% tetramethylammonium hydroxide aqueous solution, and washed with distilled water to obtain the shape of the resist pattern. -87- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

52〇464 A7 B7 π / 86, V. Description of the invention () [Sensitivity]: Define the exposure amount that can reproduce the mask pattern of 0.1 8 // m line / space = 1/1. [Resolving power]; The critical resolving power of the exposure amount which can reproduce the mask pattern of 0 · 18 # m line / space = 1/1 is defined. [Particles]; After the prepared barrier composition solution was allowed to stand at 4 ° C for 1 minute, the number of particles in the solution was counted with a particle tester manufactured by Olin Corporation. The above evaluation results are shown in Table 2. Packing-(Please read the note on the back? Matters before filling out this page). 'Line' Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is sized for the Chinese National Standard (CNS) A4 (210 X 297 mm) 520464

7 7 AB V. Description of the invention (^) Table 2 Baoshi I resin 2g acid hair 0.02g amine O.OOlg bound ΙΠ 丨 active agent 0 · _ U dry surface force 1 1 1-1 ⑴ W-1 < 5 10 0.13 2 2 1-2 (1) W-2 < 5 11 0.12 3 3 1-4 (2) W-3 < 5 16 0.13 4 4 1-8 ⑵ W-4 10 10 0.13 5 5 1-13 (3) W-1 12 13 0.13 6 6 1-18 ⑷ W-2 8 10 0.13 7 7 1-19 (1) W-3 7 10 0.13 8 8 II-7 ⑵ W-4 15 13 0.13 9 7/8 (1/1) 1-2 ⑷ W-4 < 5 8 0.12 10 6 1-6 (1) W-1 18 10 0.13 11 7 1-2 (3) W-2 < 5 9 0.12 12 8 1-2 ⑷ W-3 < 5 8 0.12 13 * 9 1-1 ⑴ W-1 < 5 15 0.13 14 * 9 1-2 (1) W-2 < 5 13 0.13 15 10 1 -4 ⑵ W-2 < 5 15 0.13 Comparative Example I 1 7 PAG-A (3) W-2 280 10 0.12 2 8 PAG-B (4) Μ / s \\ 430 12 0.15 3 1 PAG-B ⑴ W-1 480 29 0.15 4 2 PAG-C ⑴ W-2 230 33 0.15 5 3 PAG-D ⑵ W-3 350 28 0.16 6 4 PAG-E ⑵ W-4 330 63 0.18: In Examples 13, 14 A dissolution inhibitor was added, and a dissolution inhibitor A was added to the composition of Example 13, and a 3-butyl cholic acid was added to the composition of Example 14. -Packing -------- Order --------- line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs • 89- This paper size Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 520464 A7 B7 V. Description of the invention (88) As can be seen from the results in Table 2, when the positive photoresist composition of the example is excellent in sensitivity and resolution, There will be no particle generation. Further, in the comparative examples using photoacid generators not included in the general formulae (I) and (II), particles were generated. Next, the present invention of the second embodiment will be described more specifically by way of examples, but is not limited to the following embodiments in the same manner as the first invention. The resin (B) component and the dissolution inhibitor were the same as those in Example 1. [Examples 1 to 1 of 3, Comparative Examples 1 to 7] (Preparation of Orthogonal Photoresist Composition Solution) The various components shown in Table 2 were used in the amounts shown below. The resin shown in Table 2 synthesized in the above synthesis example: 2.0 g, photoacid generator: 0.02 g 'organic basic compound (amine): 0.001 g, surfactant = 0.004 g. 14% by weight was dissolved in propylene glycol monoethyl ether acetate, and then filtered through a 0.1 #m micro filter. Preparation Examples 1 to 1 3, Comparative Examples 1 to 7 positive photoresist composition solution . The amount added when a dissolution inhibitor was added was 0 ·. The photoacid generator, organic basic compound (amine), and surfactant are used as follows. Photoacid generator PAG-A (user of Comparative Example 3) ·· Triphenylsulfonium perfluoro-n-butanesulfonate-90- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ) (Please read the notes on the back before filling out this page) -install -------- order --------- line

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 520464 A7 B7 89 V. Description of the invention (Amine (1): 1,5-diazobicyclo [4.3.0] -5-nonene (2): 2, 4 , 5-Triphenylimidazoline Pack-(Please read the note on the back? Matters before filling out this page) (3): Tri-n-butylamine (4): N-hydroxyethylpiperidine surfactant W -1: Mekafak (transliteration) F1 7 6 (made by Dainippon Ink Co., Ltd.) (fluorine-based) W "2: Mekafak R08 (made by Dainippon Ink Co., Ltd.) (fluorine and polymer Siloxane type) W-3: Polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Industry Co., Ltd.) W-4: Dunroy Rolu (Transliteration) S-366 (Donroy (Chemical)) (Manufactured) (Silicon) W-5: Polyethylene oxide lauryl ether (non-ionic) W-6: Polyethylene oxide stearyl ether (non-ionic) W-7: Polyethylene glycol Dilaurate (non-ionic) -1 line · W-8: Polyethylene glycol distearate (non-ionic) (evaluation test) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The photoresist composition solution was applied on a silicon wafer using a spin coater, and Dry at 140 ° C for 90 seconds to make a positive photoresist film of about 0.5 / zm, and expose it with an ArF excimer laser (I93nm). The heat treatment after light exposure is performed at 140 ° C for 90 seconds. Developed with a 2.38% tetramethylammonium hydrogen hydride aqueous solution and rinsed with distilled water to obtain the resist pattern. [Development defect number]; Coated 0.5 # m each resist on a 6-inch Bare Si substrate -91- This paper size Applicable to China National Standard (CNS) A4 specification (210 X 297 public love) Printed by ¾ Intellectual Property Bureau employee consumer cooperative 520464 A7 B7_ 90 V. Description of the invention () Film, vacuum adsorption hot plate, at 140 ° C It is dried for 60 seconds. Then, it is exposed through a test mask of 0.35 / zm contact hole pattern (Hole Duty ratio = 1: 3) through a Nikon stepper NSR-1505505. After exposure at 140 ° C Heating for 90 seconds. After stirring and developing with 2.38% TMAH (aqueous solution of tetramethylammonium hydroxide) for 60 seconds, ethanol was washed with water for 30 seconds and spin-dried. The KLA-2112 machine was used to measure the number of development defects, and the obtained primary data was used as the number of development defects. [Sensitivity]; 0.18 line / space = 1/1 mask pattern reproduction exposure is defined. [Resolving power 1]; critical resolution that can make 0.18 / zm line / space = 1/1 mask pattern reproduction exposure Definition. [Resolving power 2]; V-line / space = 1: 1/10 pattern that can reproduce the exposure pattern of 0.18 μm line / space = 1/1 mask pattern (pattern with more space than line) ) Is defined as the critical resolution. [Sparse and Close Correlation]; In the line width of 0.18 // m branch line and space pattern (dense pattern) and isolated line pattern (sparse pattern), obtain the overlap range of each allowable focus depth of 0.18 // m ± 10%. The larger the range, the better the sparse correlation. The above evaluation results are shown in Table 3. -92- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

520464

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention) For $ v〇pv〇v〇vp \ q 00 vO pp __ i < vq MD O. Inch · Inch · r ^ jr ^ j F ·· 4 〇 〇1¾ ^ m ZD m ID S oc r— < 〇st < CT \ 00 r- 〇〇CO, < Os wn f · * ^ 〇On r ^) ο 00 inch r〇CN CNI l〇〇vD vn CM itch image power 2 1 " m), «HM ·! 〇- 丨 a r — r-; 111 1: 0.11 0.11 0.10 丨 0.11 0.10 '0.10 ♦ -i, 1-H 〇0.11 0.14 0.14 0.14 0.18 10.14 0.14 0.16 0.14 Itchy image force 1 f. Βη \) {inch one inch inch `` ~ 4 '^ -5' '. 14 »2 rS 0.134 0.13 0.14 l0.12 0.12 0.14 0.14 0.14 0.14 0.14 0.17 10.14 0.12 0.14 0.14 ΝNa £ 1 ON CO CO 0 0 CO 〇〇0 ο OJ i < 1-4 rH VO surface activity guide, 1 丨 1 0 · _ (i " H 1 CNl >: ^ /-3 1 1-1 W-2 W-3 1 W-3 W-2 1 W-2 f—H 1 W-2 W-3 1 Lotus W-4 H 1 un W-6 W-7 W-8 Ling ^). 001 g Ϊ s cn s δ cn 1 < /-N ri δ IB-4 骏 Jun generator ΐ.02g (N ^ — ^ 1 Ή OQ [B-2 ([B-3 H [B-4 < IB-5 IB -4 IIB-2 IIB-4 IB-2 IB-2 IB-1 IB-2 丨IB-3 1 cs PQ PQ PAG-A IB-1 IB-2 IB-3 resin 1 2g (CN c〇inch1 / Ί \ 〇〇〇〇〇〇ON On 0 r-. 00 f-t — CN r〇 Example II] e A r—H r < J m inch in VO r- 〇〇Os 0 嶒 *, brick f—H * CS ro »— · Comparative Example n | f 蟪 r〇_ < r \ D v〇ISJl-e Hi-Hat 1 1 Writing Risk * 5- 晷 chain thin ^ * 0-2 ^^ {«So far, < 1: Yi Huan (Please read the notes on the back before filling this page) Binding- • Cast · This paper size is in accordance with Chinese National Standard (CNS) A4 (210 χ 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 52〇464, A7 ^ -------- B7__ τ 92 5 2. Description of the invention () From the results in Table 3, it can be seen that the positive photoresist composition of the example has excellent resolution, dense pattern, and sparse pattern, and has excellent resolution, slight development defects, and small density correlation. In addition, the positive-type photoresist composition of the comparative example had many imaging defects, poor resolution of dense-patterned limbs, and large correlation between densification. [Effects of the invention] The positive photoresist composition of the present invention is particularly suitable for light in the wavelength range of far ultraviolet rays ranging from 170nm to 220nm, has excellent sensitivity and resolution, only a few particles are generated during storage, and storage stability Excellent. In addition, the problem of development defects can be substantially prevented, the correlation between density and density is small, and a good shape-blocking can be obtained. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back? Matters before filling out this page)

Claims (1)

520464 1 ^ 51, respect Λ release—ι Announcement of this model U Bulong VI. Patent application scope 89 1 243 7 1 "Positive Photoresist Composition" patent case (Amended on May 31, 2011) 6. Scope of patent application: 1. A positive photoresist composition characterized by containing at least 0.01 to 40 parts by weight of (A) at least one selected from the following general formula (for generating an acid by irradiation with active light or radiation) ( Compounds of the compounds represented by I) and (II), and 40 to 99.99 parts by weight of (B) have at least one kind of repeating unit selected from the following general formula (IaM and general formula (lb ·) and the following general A polymer having a repeating unit shown by the formula (Plant I) and having a group decomposed by the action of an acid, R4 Ra Rl2 Rl3 520464 6. Scope of patent application (In the formulae (I)-(II), K-R27 series each represent an independent hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or ring Alkoxy, hydroxyl, halogen atom, or -S-R28 group; R28 represents a linear, branched, or cyclic courtyard or aryl group; at least one of Ri ~ Ri5, Ri6 ~ Ru It is not a hydrogen atom; moreover, Ri ~ R15, R! 6 ~ R27 may be bonded by two or more to form a ring containing one or two or more kinds selected from single bonds, carbon, oxygen, sulfur, and nitrogen; X · represents RFS03_; where RF is a linear, branched, or cyclic alkyl group substituted with fluorine having 2 or more carbon atoms) —ICH-CHr- 〇 = cc = o IIXXAIR, 'AIR · (la ，) / // —c—R · Γ12 、 —— p) 丨 R Z- (in R'2 each means independent Hydrogen atom, cyano (in the formula (la1), a group, a hydroxyl group, -C00H, -C00R -C0-NH-R -C0 NH-S02-R '6, a substituted alkyl group, an alkoxy group, or a cyclic hydrocarbon group , Or the following -Y group; wherein R '5 represents a substituted alkyl group, a cyclic hydrocarbon group, or the following -Y group; R 1 6 represents a substituted alkyl group or a ring 520464 Six patent applications X-like hydrocarbon group; X represents oxygen atom, sulfur atom, -NH-, " guan302_ or -NHS02NH-; A represents a single bond or a divalent linking group; -Y group is (Wherein, r'21 to R'3. Each represents an independent hydrogen atom or an alkyl group which may have a substituent, and a, b represents 1 or 2); In the formula (lb), Z2 represents -0 or or State (1 ^ 3)-; (wherein r'3 represents a hydrogen atom, a hydroxyl group or -0S02-R'4; represents an alkyl group, a halogenated alkyl group, a cycloalkyl group or a camphor residue); ), R'M, 1 ^ 12 each represent an independent hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent; Z is a group containing two carbon atoms (CC), Atoms of alicyclic structure of substituents). 2. A positive photoresist composition, characterized in that it contains 0.001 to 40 parts by weight of (A) at least one selected from the following general formulae (IB) and (IIB) which generate an acid by active light or radiation irradiation Photoacid generator of the compound shown, 520464 VI. Patent application range of 40-99.99 parts by weight (B) has at least one kind of repeating unit selected from the following general formula Ua ') and general formula (113,) and A polymer having a repeating unit shown by the following general Θ (Π ′) and having a group decomposed by an acid action, and (C) a chlorine-based and / or silicon-based surfactant, (IB) X ' 2X (IIB) (In the formulae (IB) to (IIB): X · represents RfS03_; where 1 ^ is a fluorine-substituted linear, branched or cyclic alkyl group having 2 or more carbon atoms) to Hu 2 c—c · —X—A— R. H-, a clc— * x-A " " ~ R / V rR12 / Z 520464 6. Scope of patent application (in the formula (1 a '), h, 1? 2 each represent an independent hydrogen atom, cyano, hydroxyl, -COOH, -C00R5, -C〇-NH-R6, -C0-NH-S02-R6, an optionally substituted alkyl, alkoxy or cyclic hydrocarbon group, or the following -Y group; X represents an oxygen atom, a sulfur atom, -ΝΗ-, -NHS02 ·, or -NHS02NH -; Wherein R5 represents an alkyl group, a cyclic hydrocarbon group, or the following -Y group which can be substituted; R6 represents a substituted alkyl group or a cyclic hydrocarbon group; A series represents a single bond or a divalent linking group; -Y basis is (Wherein R21 to R3 () each represent an independent hydrogen atom or an alkyl group which may have a substituent, and a and b represent 1 or 2); In the formula (W), Z2 represents -0- or -n ( r3)-; (wherein R3 represents a hydrogen atom, a hydroxyl group, or -0S02-R4; r4 represents an alkyl group, a halogenated alkyl group, a cycloalkyl group, or a camphor residue); in the formula (II 1), Rii and Ri2 are Each represents an independent hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent; z is a group containing two carbon atoms (C-C) bonded to form a substituent that may be substituted 520464. Alicyclic structure). 3. If the positive photoresist composition of item 1 or 2 of the patent application scope, wherein the general formula (II ') is the following general formula (II'-A) or general formula (I I, -B), (IΓ-Α) (IB and B) (wherein, in the formulae (II, A) and (II, -B), R \ 3 to IΓ16 each represent an independent hydrogen atom, a halogen atom, a cyano group, -C00H, -(: 001 ^ '5 (1 ^ 5 is synonymous with the above), a group decomposed by the action of acid, -C (= 0) -XA-IT17, or an alkyl or cyclic hydrocarbon group which may have a substituent; And R ·! 3 ~ R 1, 6 are bonded to form a ring; where 'X and A are synonymous with the above; R'17 is _C0〇h, -C00R | 5, -CN, cyanide Group, alkoxy group which may have a substituent, < 〇_ NH-R '6, -C0-NH-S02-R 1 6 (R' 5, R '6 are each synonymous with the above) or -Y Η means 0 or 1) 4. The positive photoresist composition according to item 1 or 2 of the scope of patent application, wherein the RF of χ- in general formulae (I) and (II) is based on CF3 ( CF2) y (wherein 'y is an integer from 1 to 9) fluorine-substituted linear alkyl group. 5 · Positive photoresist composition according to item 4 of the scope of patent application, of which y 520464 6. Patent application The range is an integer from 1 to 7. 6. The positive photoresist composition according to item 4 of the patent application scope, wherein y is an integer from 1 to 4. 7. The positive photoresist composition of the first patent application range, wherein the component (A) is a compound having the following structure, (Where X · is synonymous with the above). 8. The positive photoresist composition according to item 2 of the patent application range, wherein (A) the photoacid generator is a compound represented by the following formula. 9. The positive photoresist composition according to any one of claims 1, 2, 5, 6, 7, and 8 in the scope of the patent application, which additionally contains a nitrogen-containing basic compound. 10. The positive photoresist composition according to any one of claims 1, 5, 6, 7, and 8 in the scope of patent application, which contains fluorine-based and / or silicon-based interfacial activity 520464. 6. Patent scope. 1 1. The positive photoresist composition according to any one of claims 1, 2, 5, 6, 7, and 8 of the scope of patent application, wherein the photoresist composition is used for irradiation of active light or radiation with a wavelength of 220 nm or less.