TW495645B - Positive-type photoresist composition - Google Patents

Abstract

Provided is photoresist compostion enabling to give a resist pattern having high resolution, no undercut, and perpendicular side walls. A positive-type photoresist composition comprises (a) a compolymer A containing at least one structural unit represented by formulae (I), (II) and (III) wherein R1 and R2, independently of each other, represent hydrogen atom or methyl group, R4 represents a alkyl, aralkyl, aryl or -Y-O-C(=O)-Z group (wherein Y represents an alkylene group having 1 to 20 carbon atoms, and Z represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms), R3 represents hydrogen atom or methyl group, and X represents a having saturated condensed polycyclic hydrocarbons or saturated bridged cyclic hydrocarbons.

Description

A7 B7 495645 j Bulletin V. Description of the Invention (1) [Technical Field] The present invention relates to a semiconductor integrated circuit element, a mask for manufacturing integrated circuits, a printed wiring board, a liquid crystal panel, etc. Resist composition. [Prior Art] The positive type photoresist composition includes chemically amplified photoresist compositions described in U.S. Patent No. 4,491,628, European Patent No. 29,139, and the like. The chemically amplified photoresist composition is a developer that emits an acid in the exposed part by irradiation with radiation such as far-ultraviolet light, and uses the acid as a catalyst to change the imaging solution for the irradiated and non-irradiated parts of the active radiation. In terms of solubility, a pattern forming material that forms a pattern on a substrate. This example is, for example, a combination of a compound that generates an acid by photodecomposition and an acetal or 0, N-acetal compound (Japanese Patent Application Laid-Open No. 48-89003), and a combination of an original ester or an acetal compound (Japanese Patent Application No. 51-120714), a polymer having an acetal or a ketal in the main chain (Japanese Patent Application Laid-Open No. 53-1 33429), an ethanol ether compound (Japanese Patent Application Laid-open No. 55-1 12995), N-fluorenimine carbonic acid compound (Japanese Patent Application Laid-Open No. 55-126236), a polymer having an original ester group in the main chain (Japanese Patent Application Laid-Open No. 56-1 7 345), and a third-order alkyl ester Compounds (Japanese Patent Application Laid-Open No. 60-3625), Silane Ester Compounds (Japanese Patent Application Laid-Open No. 60-3 0247), and Acid Compounds (Japanese Patent Application Laid-Open No. 6-30-7 5 4 9) Sho 6 0 _ 121446) and so on. These have high photosensitivity due to the principle quantum yield greater than 1. Similarly, although it is stable at room temperature over time, the paper size added in the presence of acid is subject to the Chinese National Standard (CNS) A4 specification (210 X 297 meals) (Please read the precautions on the back before filling in this Page) Binding ---- Order --------- Printed A7 by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

V. Description of the invention (2) (Please read the notes on the back before filling in this page) Thermal decomposition and alkali-soluble type, such as JP-A-Sho 59-45439, JP-A-Sho 60-3625, JP-A-Sho 62 -229242, JP 63-27829, JP 63-36240, JP 63-250642, Polym.Eng.Sce., 23 volumes, 12 pages (1983); ACS.Sym.242 Vol. 11, p. 11 (1984); Semieonductor World 1987, November Gazette, p. 91; Macromolecules, Vol. 21, p. 1475 (1988); SPIE, Vol. 920, p. 42 (1 988), etc. An acid compound, an ester or a carbonate compound in combination with a 3 or 2 carbon (for example, third butyl, 2-cyclohexene). This type has high sensitivity and has a smaller absorption in the deep-UV range than the naphthoquinonediazide / phenolic lacquer resin type, so that it is possible to obtain a type that is extremely effective in shortening the wavelength of the light source. Japanese Patent Application Laid-Open No. 2-1 9847 discloses a photoresist composition characterized by a resin containing all or part of poly (p-hydroxystyrene) phenolic hydroxyl group protected with a tetrahydropyranyl group. Japanese Patent Application Laid-Open No. 4-21 9757 also discloses a photoresist composition characterized by a resin containing 20 to 70% of poly (p-hydroxystyrene) phenolic hydroxyl group substituted with an acetal group. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Japanese Patent Application Laid-Open No. 5-249682 also discloses a photoresist composition using an acetal-protected resin. Furthermore, Japanese Patent Application Laid-Open No. 8-1 23032 discloses a photoresist composition using a terpolymer containing a group substituted with an acetal group. In addition, Japanese Unexamined Patent Publication No. 5-1 1 33667, Japanese Unexamined Patent Publication No. 6-266 1 12, Japanese Unexamined Patent Publication No. 6-289608, and Japanese Unexamined Patent Publication No. 7-209868 disclose that hydroxystyrene and (methyl) -4- Formed by acrylate copolymer This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 495645 A7 B7 ^ Description of the invention (3) Photoresist composition. Loading --- (Please read the precautions on the back before filling this page) In addition, JP-A No. 1 1-65 1 20 discloses the use of hydroxystyrene and 3-butyl (meth) acrylate and carbon Composition of (meth) acrylic acid ester copolymer of alicyclic structure with a number of 7 or more. Japanese Unexamined Patent Publication No. 10-87724 discloses a resin having an acetal group having an oxygen bond or an ester group. However, the bifurcation of these photoresist compositions in the lower part of the resist pattern is intended to improve the angle of the sidewall of the pattern in a tapered shape. [Disclosure of the invention] Therefore, an object of the present invention is to provide a positive photoresist composition having a high resolution, which can prevent the lower branch of the resist body pattern, and the sidewall angle of the pattern is vertical. In the light of the current situation, the inventor of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the inventor's research and found that the use of a resin containing at least three specific structural units and compounds containing acid generated by active light or radiation The positive photoresist composition of the solvent and the solvent can obtain a high resolution, can prevent the bifurcation of the lower portion of the resist body pattern, and can solve the problem of the taper shape of the sidewall angle of the pattern, thus completing the present invention. In other words, the positive-type photoresist composition of the present invention has the following constitution. (1) A positive photoresist composition comprising (a) a copolymer A having at least a constituent unit represented by the following general formulae (I), (II), and (III), (b) Compounds that generate acids by active light or radiation, and (c) solvents. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) A7

• ch2—9-

OH (I)

〆 CH • CHa O a R4 ^ ch2-c ^-

X (III) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (wherein in formulas (I) to (II), I and R2 each independently represent a hydrogen atom or a methyl group, and r4 represents a linear, A branched or cyclic alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a group represented by formula (IV), 0II —Y—0—C—z ( IV) (where Y represents a carbon number of 1 to 20 alkyl groups which may have a substituent, Z represents a alkyl group of 1 to 20 carbon atoms which may have a substituent, a branched or cyclic courtyard group, and may have a substituent 6 to 20 aryl groups or 7 to -20 aralkyl groups which may have a substituent), in the formula (III), 1 to 3 represents a hydrogen atom or a methyl group, and X represents a substituent. A saturated condensed polycyclic hydrocarbon or a saturated bridged cyclic hydrocarbon group which may have a substituent) (2) The positive photoresist composition according to the above (1), wherein (a) copolymer A further contains The structural unit shown by the following general formula (V). This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) Packing-(Please read the precautions on the back before filling out this page) ·-line. 495645 A7 B7 V. Description of the invention (5)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy , Methoxy or acetoxy) [Embodiments of the invention] The present invention will be described in detail below. First, the copolymer A (component (a)) having at least the structural units represented by the general formulae (I) to (III) will be described. In the positive-type photoresist composition of the present invention, the copolymer A contains a structural unit represented by the general formula (I) (hereinafter referred to as a structural unit (I)), and the general formula (11). The structural unit shown (hereinafter referred to as the structural unit (11)) and the structural unit shown below (hereinafter referred to as (III)) as a copolymer of the copolymerization component. The preferred content of each structural unit in the copolymer A, the structural unit (I) is 40 to 90 mol%, preferably 50 to 85 mol%, and more preferably 60 to 85 mol% The content of the structural unit (II) is 5 to 40 mol%, preferably 7 to 35 mol%, and more preferably 10 to 25 mol%, and the content of the structural unit (III) is 3 to 30. Molar%, preferably 5-20 Molar%, and more preferably 5-15 Molar%. Moreover, the structural unit (V) of the copolymer a

il pack --- (Please read the precautions on the back before filling out this page)-line · 495645 A7 B7 V. Description of the invention (6) The content is 5 ~ 20 mol%, preferably 5 ~ 15 mol% The more preferred is 5 to 10 mole%. The inclusion of the structural unit (V) of the copolymer A can effectively increase the dispersion and the amplitude. The system of the general formula (I) is a hydrogen atom or a methyl group, preferably a hydrogen atom. The oxy group may be substituted at any of the 2-, 3-, and 4-positions, but the 4-position is preferred in terms of sensitivity. In general formula (II), R2 is a hydrogen atom or a methyl group, and a gas atom is preferred. The acetal may be substituted at any of the 2-, 3-, and 4-positions, but the 4-position is preferred in terms of sensitivity. Examples of the linear, branched or cyclic alkyl group having 2 to 12 carbon atoms represented by R4 include ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, 3-butyl, Amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc., with ethyl, n-propyl , Isopropyl, n-butyl, 2-butyl, and 3-butyl are preferred. In addition, it is preferable that the substituent of the alkyl group is a cyclic alkyl group to be substituted at the alkyl terminal. Specifically, 2-cyclohexylethyl is preferably bonded to a cyclohexyl group at the ethyl terminal. Other substituents such as There are a hydroxyl group, a halogen atom, an amine group, a nitro group, and an acetamyl group. Among them, a hydroxyl group and a halogen atom are more preferable. The aralkyl group represented by R4 is preferably benzyl, phenethyl, styryl, cinnamyl, benzyl, tolyl, or the like. The substituent is an alkyl group having 1 to 4 carbon atoms. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, and 3-butyl are preferred. Hydroxyl, halogen atom, and amine paper sizes are applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 mm), Sang --- (Please read the precautions on the back before filling this page) · Line · Ministry of Economy Intellectual Property Printed by the Bureau ’s Consumer Cooperatives Printed by the Ministry of Economic Affairs ’Intellectual Property Bureau ’s Consumer Cooperatives’ printed 495645 A7 ____B7__ 5. Description of the Invention (7) Base, nitro, acetamyl, and methoxy are preferred. The aryl group shown is preferably a phenyl group or a naphthyl group. The substituent is an alkyl group having 1 to carbon atoms. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, and 3-butyl are preferred. A halogen atom, an amine group, a nitro group, an alkyl group such as ethenyl group, and a methoxy group are preferred. Substituents containing R4 or an ester group represented by formula (IV) are preferred. In (IV), Y represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, preferably an alkylene group having 1 to 10 carbon atoms, and specifically, for example, methylene, propylene, and alkylene Butyl, hexyl, heptyl, hexyl, hexyl, hexyl, etc. Among them, ethylene, propyl, and butyl are preferred. The above-mentioned alkylene group may have a substituent, and examples of the substituent include methyl, ethyl, propyl, butyl, phenyl, tolyl, and cyclohexyl. A linear or branched alkyl group having a carbon number of 1 to 20, preferably 7 to 20, and more preferably 9 to 18, represented by Z in general formula (IV), such as methyl, ethyl, and propyl Base, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl Base, 17-base, 18-base, etc., as well as cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclopentylethyl, cyclopentylpropyl, orthospinylmethyl, adamantane Methyl and so on. As long as the carbon number is within the range, a substituted alkyl group other than the above may be used. The cyclic alkyl group having 3 to 20 carbon atoms, preferably 7 to 20 carbon atoms, and more preferably 9 to 18 carbon atoms, as shown in the above Z, includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and hexadecyl. Hexyl, cycloheptyl, cyclohalfyl, cyclononyl, ring seventeen courtyard, -9- This paper size applies to the Zhongguanjia Standard (CNS) A4 specification (210 X 297 issued) ---- (please first (Read the notes on the back and fill out this page)

495645 A7 B7 V. Description of the invention (8) cyclooctadecyl, 4-cyclohexylcyclohexyl, 4-n-hexylcyclohexyl, pentylcyclohexyl, hexylcyclohexyl oxide, pentyl oxide cyclohexyl, 1-methyl -1-cyclohexyl, 2-methyl-1 -cyclohexyl, orthospinyl, adamantyl and the like. When the carbon number is within the above range, a ring-shaped radical other than the above may be used. The aryl group having 6 to 20 carbon atoms, preferably 11 to 20 carbon atoms, and more preferably 13 to 20 carbon atoms as shown in the above Z may be, for example, 4-methylphenyl, 4-ethylphenyl, or 2,4-dimethylamine. Phenyl, 2,4,6-trimethylphenyl, 4-th-butylphenyl, 4-cyclopentylphenyl, 4-cyclohexylphenyl, 4-cycloheptylphenyl, 4 -Cyclohexylphenyl, 2-cycloheptylphenyl, 2-cyclohexylphenyl, 2-cycloheptylphenyl, 2-cyclooctylphenyl, 3-cyclopentylphenyl, 3-cyclohexylbenzene , 3-cycloheptylphenyl, 3-cyclooctylphenyl, 4-cyclopentyloxyphenyl, 4-cyclohexyloxyphenyl, 4-cycloheptyloxyphenyl, 4-cyclooctyloxy Phenyl, 2-cycloheptyloxyphenyl, 2-cyclohexyloxyphenyl, 2-cyclopentyloxyphenyl, 2-cyclooctyloxyphenyl, 3-cyclopentyloxyphenyl, 3-cyclo Hexyloxyphenyl, 3-cycloheptyloxyphenyl, 3-cyclooctyloxyphenyl, 4-n-pentylphenyl, 4-nhexylphenyl, 4-n-heptylphenyl, 4-n-octyl Phenyl, 2-n-pentylphenyl, 2-n-hexylphenyl, 2-n-heptylphenyl, 2-n-octylphenyl, 3-n-pentylphenyl, 3-n-hexylphenyl, 3-n-heptylphenyl, 3-n-octylphenyl, 2,6- -Isopropylphenyl, 2,3-di-isopropylphenyl, 2,4-di-isopropylphenyl, 3,4-di-isopropylphenyl, 3,6-di 3-butylphenyl, 2,3-di-thi-butylphenyl, 2,4-di-thi-butylphenyl, 3,4-di-thi-butylphenyl, 2 ， 6-Di-thi-butylphenyl, 2, 3-di-thi-butylphenyl, 2,4-di-thi-butylphenyl-10- This paper size applies to Chinese national standards (CNS) A4 Specification (210 X 297 mm) Packing --- (Please read the notes on the back before filling out this page) · Line. Printed by the Consumers ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economy Printed by the Consumer ’s Cooperatives of the Intellectual Property Bureau of the Ministry of Economy Printed 495645 A7 B7 V. Description of the invention (9), 3,4-di · 3-butylphenyl, 2,6-di · isobutylphenyl, 2,3-di-isobutylphenyl , 2,4-di-isobutylphenyl, 3,4-di-isobutylphenyl, 2,6-di-third-fluorenylphenyl, 2,3-di-third-fluorenyl Phenyl, 2,4-bis-thienylphenyl, 3,4-bis-thienylphenyl, 2,6-di-isopropynylphenyl, 2,3--isopropanol Phenylphenyl, 2,4-mono * -isopropenylphenyl, 3,4-di-isofluorenylphenyl, 2,6-di-n-pentylphenyl, 2,3-di-n-phenyl Phenyl, 2,4-di-n-pentylphenyl, 3,4-di-n-pentylphenyl, 4-adamantylphenyl, 2-adamantylphenyl, 4-isobornylbenzene Base, 3-isobornylphenyl, 2-isobornylphenyl, 4-cyclopentyloxyphenyl, 4-cyclohexyloxyphenyl, 4-cycloheptyloxyphenyl, 4-cyclooctyloxy Phenyl, 2-cyclopentyloxyphenyl, 2-cyclohexyloxyphenyl, 2-cycloheptyloxyphenyl, 2-cyclooctyloxyphenyl, 3-cyclopentyloxyphenyl, 3-cyclo Hexyloxyphenyl, 3-cycloheptyloxyphenyl, 3-cyclooctyloxyphenyl, 4-n-pentyloxyphenyl, 4-n-hexyloxyphenyl, 4-n-heptyloxyphenyl, 4 -N-octyloxyphenyl, 2-n-pentyloxyphenyl, 2-n-hexyloxyphenyl, 2-n-heptyloxyphenyl, 2-n-octyloxyphenyl, 3-n-pentyloxybenzene Base, 3-n-hexyloxyphenyl, 3-n-heptyloxyphenyl, 3-n-octyloxyphenyl, 2,6-di-isopropyloxyphenyl, 2,3-di-isopropyl Phenyl oxide, 2,4-di-isopropyloxyphenyl, 3,4-di-isopropyloxyphenyl, 2,6-di-third-butyloxyphenyl, 2,3 · -3-Butyloxyphenyl, 2,4-di-3-butyloxyphenyl, 3,4-di-3-butyloxyphenyl, 2,6-di-n-butyloxy Phenyl, 2,3-di-n-butyloxyphenyl, 2,4-di-n-butyloxyphenyl, 3,4-di-n-butyloxyphenyl, 2,6-di · isobutyl Phenyloxy-11- This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

^ 5645 A7 B7 V. Description of the invention (10), 2, 3-di-isobutyloxyphenyl, 2,4-di-isobutyloxyphenyl, 3,4-di-isobutyloxyphenyl , 2,6-di-thi-thienyloxyphenyl, -I · II (Please read the notes on the back before filling out this page) 2,3-di-thi-thienyloxyphenyl, 2, 4-Di-thi-fluorenyloxyphenyl, 3,4-di-thi-fluorenyloxyphenyl, 2,6-di-isofluorenyloxyphenyl '2,3-di-isofluorenyl Phenyl oxide, 2,4-di-isofluorenyloxyphenyl, 3,4-di-isofluorenyloxyphenyl, 2,6-di-n-pentyloxyphenyl, 2, 3-di-n Amyloxyphenyl, 2,4-di-n-pentyloxyphenyl, 3,4-di-n-pentyloxyphenyl, 4-adamantyloxyphenyl, 3-adamantyloxyphenyl, 2-adamantyloxyphenyl, 4-isobornyloxyphenyl, 3-isobornyloxyphenyl, 2-isobornyloxyphenyl and the like. As long as the carbon number is within the above range, a substituted aryl group other than the above may be used. • The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints an aralkyl group with a carbon number of 7 to 20, preferably 11 to 20, and more preferably 13 to 20, such as benzyl and benzene. Ethyl, 4-methylphenylethyl, 2,4-dimethylphenylethyl, 4-cyclopentylphenylethyl, 4-cyclohexylphenylethyl, 4-hexylbenzene Ethyl, 4-¾hexylphenylethyl, 2-cyclopentylphenylethyl, 2-cyclohexylphenylethyl, 2-cycloheptylphenylethyl, 2-cyclooctylphenylethyl Base, 3-cyclopentylphenylethyl, 3-cyclohexylphenylethyl, 3-cycloheptylphenylethyl, 3-cyclooctylphenylethyl, 4-cyclopentyloxyphenylethyl Methyl, 4-cyclohexyloxyphenylethyl, 4-cycloheptyloxyphenylethyl, 4-cyclooctyloxyphenylethyl, 2-cycloheptyloxyphenylethyl, 2-cyclohexyloxy Phenylethyl, 2-cyclopentyloxyphenylethyl, 2-cyclooctyloxyphenylethyl, 3-cyclopentyloxyphenylethyl, 3-cyclohexyloxyphenylethyl, 3- Cycloheptyloxyphenylethyl, 3-cyclooctyloxyphenylethyl, 4-n-pentylphenylethyl, 4-n-12 Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 495645 A7 —------- B7__ 5. Description of the invention (11) Hexylphenylethyl, 4-n-heptylphenylethyl, 4-n-octylphenylethyl, 2-n-pentylphenylethyl, 2-n-hexylphenylethyl, 2-n-heptylphenylethyl, 2-n-octylphenylethyl, 3 -N-pentylphenylethyl, 3-n-hexylphenylethyl, 3-n-heptylphenylethyl, 3-n-octylphenylethyl, 2,6-di-isopropylphenylethyl Group, 2,3-di-isopropylphenylethyl, 2.4-di-isopropylphenylethyl, 3,4-di-isopropylphenylethyl, 2, 6-di-third -Butylphenylethyl, 2,3-di-three-butylphenylethyl, 2.4-di-thi-butylphenylethyl, 3,4-di-thi-butylbenzene Ethyl, 2,6-di-n-butylphenylethyl, 2,3-di-n-butylphenylethyl, 2.4-di-n-butylphenylethyl, 3,4-di- N-butylphenylethyl, 2,6-di-isobutylphenylethyl, 2,3-di-isobutylphenylethyl, 2,4-di-isobutylphenylethyl, 3,4-di-isobutylphenylethyl, 2,6-di-thi-thienylphenylethyl, 2,3-di-thi-thienyl Ethyl, 2,4-bis-thienylphenylethyl, 3,4-bis-thienylphenylethyl, 2,6-di-isopropylphenylethyl, 2,3-di-isopropylphenylethyl, 2,4-di-isofluorenylphenylethyl, 3,4-di-isofluorenylphenylethyl, 2,6-di-n-pentyl Phenylethyl, 2,3-di-n-pentylphenylethyl, 2,4-di-n-pentylphenylethyl, 3,4-di-n-pentylphenylethyl, 4- Adamantylphenylethyl, 2-adamantylphenylethyl, 4-isobornylphenylethyl, 3-isobornylphenylethyl, 2-isobornylphenylethyl, 4- Cyclopentyloxyphenylethyl, 4-cyclohexyloxyphenylethyl, 4-cycloheptyloxyphenylethyl, 4-cyclooctyloxyphenylethyl, 2-cyclopentyloxyphenylethyl Base, 2-cyclohexyloxyphenylethyl, 2-cycloheptyloxyphenylethyl, 2-cyclooctyloxyphenylethyl, 3-cyclopentyloxyphenylethyl-13- Paper size Applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 1 pack-(Please read the precautions on the back before filling out this page) Printed by the Employee Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs · 49 5645 A7 B7_ V. Description of the invention (U), installed --- (Please read the precautions on the back before filling out this page), 3-cyclohexyloxyphenylethyl, 3-cycloheptyloxyphenylethyl, 3-cyclooctyloxyphenylethyl, 4-n-pentyloxyphenylethyl, 4-n-hexyloxyphenylethyl, 4-n-heptyloxyphenylethyl, 4-n-octyloxybenzene Ethyl, 2-n-pentyloxyphenylethyl, 2-n-hexyloxyphenylethyl, 2-n-heptyloxyphenylethyl, 2-n-octyloxyphenylethyl, 3-n Pentyloxyphenylethyl, 3-n-hexyloxyphenylethyl, 3-n-heptyloxyphenylethyl, 3-n-octyloxyphenylethyl, 2,6-di-isopropyloxy Phenylethyl, 2,3-di-isopropyloxyphenylethyl, 2,4-di-isopropyloxyphenylethyl, 3,4-di-isopropyloxyphenylethyl, 2,6-di-3-th-butyloxyphenylethyl, 2, 3-di-th-butyloxyphenylethyl, 2,4-di-th-butyloxyphenylethyl , Line 3,4-Di-3-3-butyloxyphenylethyl, 2,6-Di-n-butyloxyphenylethyl, 2,3-Di-n-butyloxyphenylethyl Radical, 2,4-di-n-butyloxyphenylethyl, 3,4-di-n-butyloxyphenylethyl, 2,6-di-isobutylphenylphenylethyl, 2,3 -Di-isobutyloxyphenylethyl, 2,4-di-isobutyloxyphenylethyl, 3,4-di-isobutyloxyphenylethyl, 2,6-di-third -Fluorenyloxyphenylethyl, 2, 3 -di- 3rd-fluorenyl phenylethyl, 2,4-di- 3rd-fluorenyl phenylethyl, 3, Intellectual Property Office, Ministry of Economic Affairs Employees' Cooperatives printed 4-di-third-fluorenyloxyphenylethyl, 2,6-di-isofluorenyloxyphenylethyl, 2,3-di-isofluorenyloxyphenylethyl, 2,4-di-isofluorenyloxyphenylethyl, 3,4-di-isofluorenyloxyphenylethyl, 2,6-di-n-pentyloxyphenylethyl, 2,3-di -N-pentyl gasified phenylethyl, 2,4-di-n-pentyloxyphenylethyl, 3,4-di-n-pentyloxyphenylethanedamantane-phenylethyl oxide, 3- Adamantyl oxide phenylethyl, 2-adamantyl oxide phenyl ethyl-14- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 495645 A7 B7 Member of Intellectual Property Bureau, Ministry of Economic Affairs Printed by Consumer Cooperatives 5. Description of the invention (, 4-isobornyl oxide phenylethyl, 3-isobornyl oxide phenylethyl, 2-isobornyl oxide phenylethyl, etc., or the above arylalkyl Examples of the (aralkyl) alkyl group include methyl, propyl, and butyl substituents. In addition, the aforementioned linear, branched or cyclic alkyl, aryl, and other arylalkyl substituents of Z include, for example, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, Alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, n-butoxy, isobutoxy, 2-butoxy, 3-butoxy Alkoxycarbonyl groups such as alkoxy, methoxycarbonyl, ethoxycarbonyl, benzyl, phenethyl, cumyl, aralkyl, aralkyloxy, formamyl, ethenyl , Butylamino, phenylfluorenyl, cyanoyl, pentyl, and the like, fluorenyl and the like, butyloxy, and the like, alkenyl, vinyloxy, allyloxy, allyloxy, and butenyloxy Alkenyloxy such as aryl, aryloxy such as aryl, phenoxy, and aryloxycarbonyl such as phenylfluorenyl. By keeping the carbon number in a better range, the fixed wave or imaging defect can be significantly improved. Therefore, effects different from those described in Japanese Patent Application Laid-Open No. 10-87724 can be obtained. Specific examples of the base represented by the general formula (IV) are shown below, but are not limited thereto. -15- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 χ 297 mm) (Please read the notes on the back before filling out this page) Line 495645 A7 B7 V. Description of Invention (M Intellectual Property of the Ministry of Economic Affairs Printed by Bureau Consumers Cooperative

(Please read the precautions on the back before filling this page) This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 495645 A7 B7 V. Description of invention (β printed by Employee Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs) system

(Please read the precautions on the back before filling out this page) The paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) 495645 A7 B7 V. Description of the invention (4) ~. ηΓ ~. r〇 0 〇 U II 0 0 ～. r〇 丫 0 η installed · 11 (Please read the precautions on the back before filling out this page). Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Online Economics 18 _ This paper size applies to China National Standard (CNS) A4 specifications (210 χ 297 mm) 495645 A7 B7 V. Description of Invention (7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

(Please read the precautions on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 495645 A7 B7 V. Description of the invention (19) r3 series in general formula (III) Is a hydrogen atom or a methyl group. --- (Please read the notes on the back before filling this page) X is a saturated condensed polycyclic hydrocarbon group which may have a substituent or a saturated bridged cyclic hydrocarbon group which may have a substituent. The saturated condensed polycyclic hydrocarbon group is preferably a saturated condensed polycyclic nicotyl group having a carbon number of 9 to 20, such as perhydrogenated section, perhydronaphthalene, pervaporated Austria, pervaporated heptene, perhydrobiphenyl, perhydrogenated. Benzoindene, perhydrone, perylene hydrogen peroxide, phenanthrene perhydrogen, fluoranthene perhydrogen, 1,2-phenanthrene perhydrogen, and the like are not limited thereto. The saturated condensation polycyclic hydrocarbon group preferably has 2 to 4 rings. The substituent is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, an amine group, or the like. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints saturated bridged cyclic hydrocarbon groups with saturated bridged cyclic hydrocarbon groups having 7 to 20 carbon atoms. For example, there are adamantyl, methyladamantyl, ortho-alkyl, methyl-ortho-alkyl Alkyl, isobornyl, 2-orthospinylmethyl, 3-methyl-2-orthospinylmethyl, 4-pentylbicyclo [2,2,2] octyl, 1-adamantane Methyl, 1-adamantylethyl, tricyclic [5.2.1. 02'6] decyl, tetracyclic [6.2. 1. 13'6.02, 7] dodecyl, hexacyclic [6.6.1.13 , 6.11 (), 13.02,7.09, 14] Heptadecyl, etc., but not limited by these. The number of saturated bridged cyclic hydrocarbon groups is 2 to 8, especially 2 to 6, with carbon atoms at the head of the bridge (two third carbon atoms shared by the two rings when connected by a carbon atom bridge). Among these, especially in terms of resolution, adamantyl, orthospinyl, isobornyl, tricyclo [5.2. 1.02,6] decyl, tetrahydro [6.2.1.13,6.02,7] alkyl. Substituents are straight-chain, branched-chain alkyl, hydroxy, and halogen having 1-4 carbon atoms

-21-continued on the 19M This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 495645 A7 B7 V. Description of the invention (20) Atoms, amines, etc. In addition, in the structural unit represented by the general formula (V), '1 ^' represents a hydrogen atom or a methyl group, R represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, and methoxy group. Or ethyl. The substitution position of R is the 2-, 3-, and 4-position, and the 4-position is preferred. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a 2-butyl group, a 3-butyl group, and the like, and a methyl group and a 3-butyl group are preferable. When the weight-average molecular weight of the copolymer A is measured by gel permeation chromatography and molecular weight (Mw) in terms of polystyrene, it is preferably 2,000 to 1,000,000, more preferably 2,000 to 500,000, and most preferably 20,000 ~ 30,000. If the molecular weight is 2,000 or less, the reduction of the barrier film is extremely large, while if it is more than 1,000,000, the solubility deteriorates and the resolution decreases. A more specific structure of the copolymer A is shown below, but the present invention is not limited thereto. In the following specific examples, Et represents ethyl, 3-Bu, or 3-butyl, and Ac represents ethenyl. (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-22- This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 cm) 495645 A7 B7 V. Description of the Invention (H) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

-23- (Please read the precautions on the back before filling this page) This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 495645-A7 ______B7 V. Description of Invention (") Intellectual Property of the Ministry of Economic Affairs Printed by Bureau Consumers Cooperative

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

495645 50 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

This paper size applies to Chinese National Standard (CNS) A4 (210 χ 297 mm) (Please read the precautions on the back before filling this page)

495645-A7 ____B7 V. Description of Invention (Μ) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

(Please read the precautions on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) -26- 495645 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs DESCRIPTION OF THE INVENTION (25) The photoacid generator (b) used in the present invention is a compound that generates an acid by irradiation with active light or radiation. The compound used in the present invention to generate an acid by irradiation with active light or radiation can use a photoinitiator, a photoinitiator, a photoinitiator, a photochromic agent, and a photochromic agent. Or conventional light used by 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 compounds used in the present invention to generate acid by irradiation with active light or radiation are, for example, SIschle singer, Photogr_Sci. Eng., 18,387 (1974), TSBal et al, Polymer, 21,423 (1 980), etc., the ammonium salts described in U.S. Patent Nos. 4,069,055, the same as 4,069,056, the same as 27,992, the Japanese Patent Application No. 3-140140, DCNecker et al, Macromolecules, 17 »2468 ( (1984) 'CSWen et al, The, Proc. Conf. Rad Curing ASIA, p. 478 Tokyo, Oct (1988), U.S. Patent No. 4.069,055, Phosphonium Salt described in No. 4,069,056, JVCrivello et al, Macromorecules, 10 (6), 1 307 (1 977), Chem. & Eng. News, Nov. 28, p. 31 (1 988), European Patent No. 1 04,143, same as 339,049, same as 410,201 Ferric iodide as described in Japanese Patent Application Laid-open No. 2-1 50848, Japanese Patent Application No. 2-296 5 14 and the like, JVCrivello et al, Polymer J. 17, 73 (1 985) 'JVCrivello et a 1, J. Org. Chem., 43, 3055 -27- (Please read the notes on the back before filling this page) Standard (CNS) A4 specification (210 X 297 mm) 495645 A7 B7 V. Description of invention (26) (1978) 'WR Watt et al, J. Polymer. Sci., Polymer Chem. Ed., 22, 1789 (1984 ), JVCrivello et al,

Polymer Bull., 14,279 (1985), JVCrivello et al, Macromorecules, 14 (5), 1141 (1981) 'JV, Crivello et al, J. Polymer. Sci., Polymer Chem. Ed., 17, 2877 (1 979), European Patent Nos. 370,693, same as 161,811, same as 410,201, same as 339,049, same as 233,567, same as 297,443, same as 297,442, US Patent No. 3,902,114, same as 4,933,377, same as 4,760,013, same as No. 4,734,444, No. 2,83 3,827, German Patent No. 2,904,626, No. 3,604,580, No. 3,604,581, etc., JVCrivello et al, Macromorecules, 10 (6), 1307 (1977) 'JVCrivello et al, J. Polymer. Sci., Polymer Chem. Ed., 17, 1047 (1 979) and other selenium salts, CSWen et al., The, Proc. Conf. Rad. Curing ASIA, p. 478 Tokyo , Osmium salts such as arsenic salts as described in Oct (1988), U.S. Patent No. 3,905,81 5; Kai Sho 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62-21 2401, JP Organic halogen compounds described in 63-70243, JP-A-63-298339, etc., K. Meier et al, J. Rad. Curing, 13 (4), 26 (1986) 'TPGill et al, Inorg.Chem ., 19,3007 (1980) 'D. Astruc, Acc. Chem. Res., 19 (12), 377 (1896) -28- This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) ) K Pack-(Please read the precautions on the back before filling out this page) Order · · · Line · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7

V. Description of the invention (27) Organometallic / organohalide printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, JP-A No. 2-1 61 445, etc., S. Hayase et al, J. Polymer Sci., 25,753 ( 1987) 'E. Reichmanis et a 1, J. Polymer Sc i., Poyme r Chem. Ed., 23, l (1985)' QQZhu et al, J. Photochem., 36, 85, 39,317 (1987) ' B. Amit et al, Tetrahedron Le 1 1., (24) 2205 (1 973) 'DHR Barton et al, J.

Chem. Soc., 3571 (1965) 'P.M.Collins et al, J.

Chem. Soc., Perkin 1, 1695 (1975), M. Rudinstein et al, Tetrahedon Lett., (17), 1445 (1975), JWWalker et a 1, J. Am. Chem. Soc., 11 0, 7170 (1 988) 'SC Busman et al, J. Imaging Technol., 11 (4), 19 1 (1 985)' HMHoulihan et a 1, Macromo1 ecu 1es, 21, 2001 (1988) 'PMCollins et al J. Chem. Soc.,

Chem. Commun., 532 (1972), S. Hayase et al,

Macromo1ecu1es, 1 8,1 799 (1 985) 'E. Reichmanis et al, J. Electrochem.Soc., So 1 id State Sci. Techno 1., 130 (6)' FMHoulihan et a 1, Macromo1ecu1es, 21, 2001 (1 988), European Patent No. 0290,750, Same No. 046,083, Same No. 56,535, No. 271,851, Same No. 0,388,343, US Patent No. 3,901,710, Same No. 4,181,531, Special Photogenerating agents with ortho-nitrobenzyl type protecting groups as described in Kaisho 60-1 98 5 38, JP 53-1 33022, etc., M.TUNOOKA et al, Polymer Preprints Japan, 35 (8 ) 'G. Berner et al, J. Rad .. Curing, 13 (4), WJMijs et al, Coating Technol, 55 • 29- This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) ) '(Please read the notes on the back before filling out this page)

A7 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^^^ _ BZ____ V. Description of Inventions (28) (697), 45 (1 983) '' Akzo.H. Adachi et al, Polymer Preprints, Japan, 37 (3) , European Patent No. 0199,672, Same No. 84,515, Same No. 04,115, Same No. 618,564, Same No. 0101,122, US Patent No. 4,371,605, Same No. 4,431,774 JP 64-18143 JP-A No. 2-245756, JP-A No. 3-140 1 09 and other typical photodecomposition compounds that generate sulfonic acids, such as sulfamates, and JP-A 61-166544 and other di-maple compounds . In addition, for example, M.E. can be used to generate an acidic group by light or to introduce a compound into a main or side chain of a polymer.

Woodhouse et a 1, J. Am. Chem. Soc., 104, 5586 (1982) SPPappas et al, J. Imaging Sci., 30 (5), 21 8 (1986), S. Kondo et al, Makromol. Chem., Rapid Commun., 9, 625 (1 988) 'Y. Yamada et a 1, Makromo 1. Chem., 152, 153, 163 (1972)' JVCrivello et al., J. Polymer Sci., Polymer Chem. Ed., 1,7,845 (1,979), U.S. Patent No. 3,849,137, German Patent No. 3914407, Japanese Patent Application No. 63-26653, Japanese Patent Application No. 55-164824, Japanese Patent Application No. 62-69263 , Compounds described in JP-A-Sho 63-1 46038, JP-A-Sho 63-1 63452, JP-A-Sho 62-1 53853, JP-A-Sho 63-146029 and the like. Alternatively, NRPillai, Synthesis, (1), 1 (1980), A. Abad et al, Tetrahedron Lett., (47) 4555 (1971) 'DHR Barton et al, J. Chem. Soc., ( C), 329 (1970), U.S. Patent No. 3,799,778 and European Patent No. 126,712 are compounds that generate light by light. The following explains the use of the above-mentioned by active light or radiation • 30- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page )

495645 A7 ____ B7____ V. Description of the invention (29) Among the compounds that produce acid by irradiation with radiation, it is particularly effective. (1) A trihalomethyl substituted triazine derivative represented by the following general formula (PAG 1) or an S-triazine derivative represented by the general formula (PAG2).

RN—N // \\ person / C, 201 (PAG1) Nan⑺3 R202 human Λ (Y) 3c NC (Y) 3 (PAG2) (wherein R2 (H represents a substituted or unsubstituted aryl, alkene R represents an unsubstituted or unsubstituted aryl group, a storage group, a radical, _ C (γ) 3. Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention Not subject to these. 202 (Please read the notes on the back before filling out this page)

Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 495645 A7 B7 V. Description of the invention (ΜΝΝΝ Cl " \ j-CH = CH ~ CN〇C ~ CC13 (PAG1 -1) _ Ν—N CH3 meaning) -CH = CH-C, 〇 / O CC13 (PAG1 — 2)

CH3O 〇N—N // \\ CH = CH-C C-CBr3 (PAG1-3) (Please read the notes on the back before filling this page) (n) C4H90 〇N—N // \\ CH = CH —CC-CCI3 (PAG1-4) 0

N—N // \\ CH = CH-CC-CCI3, 0, (PAG1-5) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, C C-CCI3, 〇 (PAG1-6) N—N // \ \. • CH = CH-CC-CCI3 nrv < (PAGl-7) 〇-ch = ch〇- N—N // \\ CH = CH-CC-CC13 (PAGl-8) This paper standard applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) -32- 495645 A7 B7 V. Description of invention (y CC13 CI3C human N CCl3 • (PAG2-1)

C13C

N CC13 (PAG2-2)

(PAG2-3)

(PAG2-4) (Please read the notes on the back before filling this page)

(PAG2-5),

COCH3 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

N C13C people here (PAG2-7) (PAG2-6)

(PAG2-8) -33- Paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm 495645 Α7)

(PAG2-10) (2) An iodonium salt represented by the following general formula (PAG3) or a phosphonium salt represented by the general formula (pAG4). κ (PAG3) ZZ ·

R R 204 203 One S + ZO — Outfit — (Please read the notes on the back before filling this page) Order

R 205 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (PAG4) (where Ar1 and Ar2 represent independent substituted or unsubstituted aryl groups, and the preferred substituents are alkyl and halogenated alkyl , Cyclic alkyl 'aryl, alkoxy, nitro, carboxyl, alkoxycarbonyl, hydroxyl, thiol, and halogen atoms. R2O3, R2O4, and R2O5 each represent an independently substituted or Unsubstituted alkyl group and aryl group. Preferred are aryl group having 6 to 14 carbon atoms, courtyard group having 1 to 8 carbon atoms and substituted derivatives thereof. The preferred substituent group has carbon for the aryl group. Alkoxy groups having 1 to 8 carbons, alkyl groups having 1 to 8 carbon atoms, nitro, carboxyl, hydroxyl, and halogen atoms. For alkyl groups, there are alkoxy groups having 1 to 8 carbon atoms, carboxyl groups, and yloxy groups. -34- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) line 495645 A7 B7 V. Description of the invention (33) Z-series means anion, such as BF4 ·, AsF6_, SbF6 -、 (Please read the notes on the back before filling this page)

SiF6_ 'SiF6_, C104_, CF3S03_ and other polyfluorinated aromatic sulfonic acid anions, anthraquinone sulfonic acid anions, anthraquinone sulfonic acid anions, etc. Dyes and the like, but the present invention is not limited by them. In addition, at least two of R2Q3, R2.4, and R2Q5 and Ar1 and Ar2 may each be a single bond or linked through a substituent. Further, a photoacid generator having a small change in performance over time (T-Top formation, line width change, etc.) after the heat treatment after exposure is preferred. The photoacid generator is, for example, Ar1, Ar2, R2G3 to R205 in the general formulae (PAG3) and (PAG4) above, which represent a substituted or unsubstituted aryl group, and Z-series is in a resist film when an acid is generated by light irradiation. Less diffusive. Specifically, the 2-series means having at least one alkyl or alkoxy group selected from branched or cyclic carbons of 8 or more, or having at least two selected from branched, branched, or cyclic carbons. Benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having 4 to 7 alkyl or alkoxy groups, or having at least 3 selected from linear or branched carbons having 1 to 3 alkyl or alkoxy groups Anion. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, for example, the compounds shown below, but the present invention is not limited by these. -35- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 495645-A7 _____B7 V. Description of Invention (Μ) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 0 ~ i + _h0 bf " (PAG3 -1) α-ι + -ο pf6- (PAG3-2) 0 ~ i + _0 asf 「(PAG3-3) *

SbF6 " (PAG3-4) -36- This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) (Please read the precautions on the back before filling this page)

495645 A7 B7 V. Description of the invention (β) 〇zN_ ^ -i + -Q N02 CF3S03 (PAG3-5) Q-i + -〇-〇cH3 pFe (PAG3 — 6) ^^-1+ 1〇CH3 SbF6 (PAG3 — 7) pf6 '(PAG3-8) No. 2 CF3SO3 (PAG3-9) (Please read the precautions on the back before filling this page)

H3C

CH3 AsF6. Printing of clothing by employees' cooperatives in the Intellectual Property Bureau of the Ministry of Economic Affairs (PAG3 -10)

SbF6_ (PAG3-12)

Cl ~ ^:

Cl pf6 '(PAG3 -13) 37- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 x 297 mm) 495645. A7-· B7 Printed Invention Note by Employee Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs (w) f3c-〇-i + -v / ~ cf3 cf3s〇3 (PAG3-14) PF6 *

Cl pf6

tBu ~ Y ^ y—n SbF6 (PAG3-17) i ~ 0 ~]

tBu ^ \ _ n, -tBu (PAG3-18)

Cl (PAG3-20) 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) PF6 * pf6. CF3S〇3. • 38— 495645 A7 B7 V. Description of the invention (W)

CF3SO3 0 ~]

(PAG3 — 22)

〇CE3 0 ~ ι + Ό

o3s- \ / -OC2H5 (PAG3-23) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs α-

* 39— (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) 495645-A7 B7 V. Description of the invention (> (n) HnC5

(PAG3-26) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

(PAG3 — 27) -40- (Please read the notes on the back before filling this page)

This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 495645 Α7 Β7 V. Description of the invention (π

S

Q -'- O

O'-O H17Ce O ^ s〇3 · (PAG3-28) H25CirQ- < > -SO, (PAG3-29) H9C < 1h, c4, 1 H, C / -SO / (PAG3-30) 0 «C | Hi7 Hi7C.-o-^^-so3 · (PAG3-31) (Please read the precautions on the back before filling this page) C, H9l nHsCr0- ^ y-S03 · (PAG3-32) ^ O door OC4Hs n He〇r〇 "^ -s〇3 'C > C4Hsn (PAG3-33) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, ch3 H3C— ^ y-S03 ^ CH3 (PAG3-34) -41- present Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) C ^ i-hO h9c,

S〇3 1 h9cv% (PAG3-35) 495645 A7 B7 V. Description of the invention ^ H, C. _ 〇 * -〇lH17Ct-0-^^ S03 * W Factory (PAG3-36) (PAG3-37) OK ) 1 Η Γ SO, so / ri -4 n C / tHsC ^ (PAG3-38) o (PAG3-39) Cl η h3c-o- • och3 'Hn7cr0 Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs

(PAG3-40) -42- (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) 495645 /-A7 B7 V. Description of the invention (w bf4 (PAG4 -1) ot- S · PF6 1 (PAG4-2) • S 10 AsF6 · (Please read the notes on the back before filling in this page) S 十 CF3S〇3 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (PAG4-3)

SbF6, (PAG4-4)

Or (PAG4-5) • s + C8F17S〇3. (PAG4-6), OtS. (PAG4-7)

F F

This paper size is applicable to China National Standard (CNS) A4 (210 x 297 mm) 495645 A7 B7 V. Description of the invention (4 >)

H3C-〇-sx-OC2H5J CF3S〇3 (PAG4-8) h3co-^^-s

Cl lz CF3SC3 (PAG4-9) h〇- \ ch3 (PAG4 -10) ΡΓ6 * (Please read the precautions on the back before filling this page)

SbF6 · (PAG4-11)

HO BF4 Printed Clothing for Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (PAG4 -12)

H3co (PAG4 -13) -44- CF3SO3 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 495645 A7 B7 V. Description of the invention (〇 (n) C4Kg H〇- ^ \ ~ S ( n) C4Hg

pf6 '(PAG4 -14)

HO ch3 (PAG4-15) BF4 (Please read the precautions on the back before filling this page)

pf6

AsFg '

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (PAG4-17)

O8F17SO3

(PAG4-18) This paper size applies to Chinese National Standard (CNS) A4 (210 x 297 mm) _45_ 495645 A7 B7 V. Description of the invention (β) α〇C-CHZ-S 十 -CH3 SbF6-CH3 (PAG4 -19) 〇 ^ c-ch2-s ^] (PAG4-20) pf6 (Please read the precautions on the back before filling this page) a 〇c-ch2-s

AsF6. (PAG4-21)

Cl 〇 II C-CH2-s ·

AsF6 (PAG4-22) 〇 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ C-CH2-sJJ > (PAG4-23) 〇I! C-CH2-s (PAG4 — 24) This paper standard applies Chinese national standards ( CNS) A4 size (210 x 297 mm) pf6 ·

AsFg '—46 · 495645 A7 B7 V. Description of the invention (β V / 〇 II 丄 OCH2-S ·-(n) C4H9 (n) C4Hg (PAG4-25) PF6

C8H17SO3 (PAG4-26) O ^ s-O ~ s'

SbF6 (Please read the notes on the back before filling this page) (PAG4-27)

S 2CF3SO3

S 2AsF6. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (PAG4 — 29)

S03

OC2H5 • 47- This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 495645 A7 B7 V. Description of invention (A)

1 2 Η c one 3 Η IC SIC

(PAG4-32)

F.

F

f y F F

• S.

(PAG4 — 34) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs _48 · (Please read the precautions on the back before filling this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 495645-A7 B7 Printed clothing by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (47) 〇g H, 7C < ^ s〇 3- H0-Q4: 'η, 7ο, .〇η〇 ^ 5〇3 (PAG4-35) 0 (PAG4-36)

so / so. o-cah; (~ Vs + HsCr0 ^ yS〇i ό. (PAG4-41)

OC.H Gate

S03

• 49. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) so. (Please read the precautions on the back before filling this page)

495645 A7 B7

5. Description of the invention (W

SO,

(PAG4-43)

OH

so n h9ca-o \} -oc4h9 • 9. 〇-S " 0-f 'Hi7C «-〇hQ-SO'0 (PAG4-44) (PAG4-45)

Printed by C / f c2hso ^ Q-so3 · (PAG4-47) -50 · (Please read the precautions on the back before filling this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 495645 A7 B7 ___ V. Description of the invention (49) The above phosphonium salts shown in the general formulas (PAG3) and (PAG4) are known substances `` For example, JWKnapczyk et al, J. Am. Chem. Soc., 91, 145 (1969), AL Maycok et al, J. Org. Chem., 35, 2532, (1970) '' E. Goethas et a 1, Bu11.Soc.Chem. Be 1g., 73, 546, (1964) " HMLeicester. J. Am. Chem. Soc., 51, 3587 (1929) 'JVCrivello et al., J. Polym .Chem.,

Ed., 18, 2677 (1980), U.S. Patent No. 2,807,648, and the methods described in 4,247,473, JP 53-101,331 and the like. (3) A dimaple derivative represented by the following general formula (PAG5) or an iminosulfonate derivative represented by the general formula (PAG6). ------- l · 丨 丨 Installation -------- Order · (Please read the precautions on the back before filling in this page)

ArJ-S〇2-S〇2 — Ar (PAG5) input

r206-s〇z-〇-n A (PAG6)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (where 'Ar3, Ar4 each represents an independent substituted or unsubstituted aryl group, and R2 () 6 represents a substituted or unsubstituted alkyl group, aromatic group (A is a substituted or unsubstituted alkylene, alkenyl, or arylene). Specific examples include the following compounds, but the present invention is not limited thereto. -51- This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) 495645 A7 B7 V. Description of the invention (θ)

Cl -〇-S〇2-S02-Q- (PAG5 -1)

Cl H3C-^^-S〇2-S02-^^ CH3 (PAG5-2)-^-S02 a so2 ^^^-och3 (PAG5-3) H3C " ^^^ S02-S02-^^ " C1 (PAG5-4) F3C-^^ S〇2-S02H ^ k CF3

H3CO (PAG5-5) (Please read the notes on the back before filling this page)

S〇2 ~ * S〇2

Cl Printed by Employee Consumer Cooperative of Intellectual Property Bureau of Ministry of Economy H5C2〇

S〇2-S〇2 (PAG5-7) (PAG5-6)

Cl S0 2-S02 (PAG5-8)

Cl-52- This paper size is in accordance with China National Standard (CNS) A4 (210 x 297 mm) 495645 A7 B7 May 1 丨 · Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

Cl

S〇2 ~ S02- ^ / Γ ^ Η3 (PAG5-9) S〇2-S〇2 〇CH3 (PAG5-10)

Cl 乂 少 " SO?-S〇2

och3 (PAG5-11) H $ > 〇S〇2-S〇2 h3c

(PAG5 -12) (Please read the notes on the back before filling this page)

F F

F F

S〇2-S〇2 —, IrY F F F F (PAG5-13)

s〇2-s〇2— (PAG5 -14) -53- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 495645 A7 B7 V. Description of the invention (

0 N one 0 — 〇 (PAG6-1) 0

CH3 0 ^ / 1 0-S〇r ^^ OCH3 0 (PAG6-3) 0

^ N-0-S〇2-^^ CF3 〇 (PAG6-4) (Please read the precautions on the back before filling out this page) The Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption Cooperative, printed sashimi 0

〇CH3 · .54 · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

〇

〇

495645-A7 B7 V. Description of the invention (θ-101-S02-CgHs 0 (PAG6-7) n ~ o-so2-^^ 〇 (PAG6-8) N-0-S〇2-^^ 〇 ( PAG6-9) (Please read the notes on the back before filling this page)

(PAG6-10) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

(PAG6 -12) -55- This paper size is applicable to Chinese National Standard (CNS) A4 (210 x 297 mm) ^^ 0045 A7 B7 V. Description of the invention (54

F

Packing --- (Please read the precautions on the back before filling this page) In the present invention (b) Compounds that generate acid by active light or radiation are sulfonium salt, second mill, and 4-position DNQ (diazide naphthalene Quinone) sulfonate and triazine compounds are preferred, and at least one sulfonium salt is more preferred. The addition amount of these (b) compounds that generate acid by active light or radiation is based on the total weight of the positive photoresist composition of the present invention (except for the coating solvent), which is usually 0.001 to 40% by weight, It is preferably 0.01 to 20% by weight, and more preferably 0 to 1 to 5% by weight. If the amount of the compound that is decomposed to generate an acid by irradiation with active light or radiation is less than 0.01% by weight, the sensitivity is low, and if it is more than 40% by weight, the light absorption of the resist is too high and the appearance is not good. Or the scope of the project (especially baking) is too small to be desirable. -Line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy -56- 495645 A7 V. Description of the invention (55) Organic basic compounds can be used in the composition of the present invention. Therefore, it is not desirable because the stability during storage is improved and the change in the line width by pED is small. The preferred organic basic compounds used in the present invention are compounds which are more sensitive than phenol. Among them, a nitrogen-containing basic compound is preferred. A preferable chemical environment has, for example, the following formulae (A) to (E). R251 R250-N-R252. (A) (wherein 'R25Q, R251 & R252 may be the same or different carbon atoms, a carbon number of i ~ 6, an amino group of carbon number 1 ~ 6, a carbon number of 1 Hydroxy group of ~ 6 or substituted or unsubstituted aryl group of 6 to 20 carbon atoms, and R25i and R2 5 2 can be bonded to each other to form a ring) (Please read the precautions on the back before filling this page) • N—C = N · N = C- = U- " (B) " (C) • (D) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs R254 R255 R253 I ... (E) II R253 in the above formula (E) , R254, R255 and R256 may be the same or different alkyl groups having 1 to 6 carbon atoms. In addition, the preferred compound is a nitrogen-containing basic compound having two or more nitrogen atoms in different chemical environments in one molecule, and the more preferred is a compound containing -57- paper. Applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 495645

A7 V. Description of the invention (56) The substituted or unsubstituted amine group and the nitrogen atom constitute two kinds of compounds or compounds having an alkylamine group. Preferred examples are, for example, substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted Substituted imidazole, substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or Unsubstituted pyrazoline, substituted or unsubstituted piperidine, substituted or unsubstituted morpholine, substituted or unsubstituted aminomorpholine, and the like. Preferred substituents are amine, amine alkyl, alkyl amine, amine aryl, aryl amine, alkyl, alkoxy, fluorenyl, fluorenyl, aryl, aryloxy, nitrate Radical, meridian, cyano. More preferred compounds are, for example, dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-methylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3 -methylpyridine, 2-amino-4_methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 3-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-pyranylpiperidine 2, iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-pair -Tripyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3 -Pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, etc., but not limited thereto. -58- This paper size is in accordance with Chinese 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 495645 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (57) These nitrogen-containing basic compounds can be used alone or in combination of two: i :. The amount of the nitrogen-containing basic compound to be used is usually 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, for 100 parts by weight of the photosensitive resin composition (excluding the solvent). If it is less than 0.001 parts by weight, the above effects cannot be obtained. In addition, if it is more than 10 parts by weight, the sensitivity tends to decrease and the developability of the non-exposed portion tends to deteriorate. The chemically amplified positive photoresist composition of the present invention may further contain a surfactant, a dye, a pigment, a plasticizer, a photosensitizer, and two or more of the solubility-enhancing properties of the developing solution as required. Compounds such as phenolic OH groups. Specific examples of suitable surfactants include polyethylene oxide alkylene oxide, polyethylene oxide stearyl ether, polyethylene oxide hexadecyl ether, polyethylene oxide oleyl ether, and the like. Ethers, polyethylene oxide alkyl aryl ethers, such as polyethylene oxide octyl phenol ether, polyethylene oxide nonyl phenol ether, polyethylene oxide · polypropylene oxide block copolymers Class, sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, sorbitol monostearate Esters such as sorbitol fatty acid esters, polyethylene oxide sorbitol monolaurate, polyethylene oxide sorbitol monopalmitate, polyethylene oxide sorbitol monostearate, Non-ionic surfactants such as polyethylene oxide sorbitol trioleate, polyethylene oxide sorbitol tristearate, and other polyepoxide sorbitol fatty acid esters, Yebu Dunpu (Transliteration) EF301, EF303, EF3 52 (made by Shin Akita Kasei Co., Ltd.), Mekafak (transliterated) F171, F173 (made by Dainippon Ink Co., Ltd.), husband Rollaton FC430 -59- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) '~ --Packing ... (Please read the precautions on the back before filling this page). 495645 A7 B7 V. Description of the invention (58), FC431 (Sumitomo Shrimiya (transliteration) (share) system), Asahi Carton (transliteration) AG710, Safron S-382, SC101, SC102, SC103, SC104,-equipment --- (Please read the precautions on the back before filling out this page) Fluorine surfactants such as SC105, SC106 (made by Asahi Glass), KP341 (based on Shin-Etsu Chemical Co., Ltd.) Made) or acrylic or methacrylic (co) polymerized poly-Fro No. 75, No. 95 (made by Kyoeisha Oil Chemical Industry Co., Ltd.) and so on. These surfactants may be added singly or in combination. The preferred addition amount is 0.0005 to 0.01 parts by weight for 100 parts by weight of the composition (excluding the solvent). Line · Suitable dyes are oily dyes and basic dyes. Specific examples are oil yellow # 101, oil yellow # 103, oil pink # 312, oil green BG, oil blue B0S, oil blue # 603, oil black BY, oil black BS, oil black T-505 (the above is Eury Enton Chemical Co., Ltd.), Crystal Violet (CI 42555), Methyl Violet (CI42535), Basic Core Red B (CI45170B), Malachite Green (CI42000), Methylene Blue (CI 5201 5), etc. In addition, by adding the following spectroscopic sensitizer, and not absorbing the photoacid generator used, and sensitizing it by ultraviolet rays in a long wavelength range, the invention can be printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs The chemically-amplified positive-type resistor has sensitivity to the i or g line. Specific examples of suitable spectral sensitizers include benzophenone, P, P · -tetramethylaminobenzophenone, p, p'-tetraethylethylaminobenzophenone, 2-chloride Thioxanthone, ketanone, 9-ethoxyl, 10,000, yuan, phenanthrene, phenothiazine, benzyl, acridine tangerine, benzoflavin, acetoflavin-T, 9, 10-diphenyl Anthracene, 9-fluoren, acetophenone, phenanthrene, pyrene, p-benzoquinone, 2-chloro-4-nitroaniline, N-ethylfluorenyl-p-nitroaniline, p-nitroaniline, N-ethyl醯 基 -4- -60- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ^ 645 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7: I —________ V. Description of the invention ( 59) nitro-1-naphthylamine, bitter amine, anthraquinone, 2-ethylanthraquinone, 2-third 3-butyl 1: quinone, 1,2-benzoanthraquinone, 3-methyl-1, 3-diazo-1,9-benzoxanthone, diphenylacetone, 1,2, naphthoquinone, 3,3, -carbon-bis (5,7-dimethoxycarbon coumarin ) And hexabenzobenzene, etc., but not limited by these. Examples of compounds having two or more phenolic hydroxyl groups that promote solubility in a developing solution include polyhydroxy compounds, and preferred polyhydroxy compounds include phenol, resorcinol, fluorinated grape acid, fluorinated saccharin, 2 ,, 3,4-trihydroxybenzophenone, 2,3,4,4; -tetrahydroxybenzophenone, α, α ,, α ”-Shen (4-hydroxyphenyl) -1,3,5 -Triisopropylbenzene, ginseng (4-hydroxyphenyl) methane, ginseng (4-hydroxyphenyl) ethane, 1,1'-bis (4-hydroxyphenyl) cyclohexane. Chemical Amplification of the Invention Type positive photoresist compositions are those in which the above components are dissolved in a solvent (d) and coated on a carrier. The solvents that can be used are ethylene dichloride, cyclohexanone, cyclone ketone, 2- Heptone, r-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ketone, 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, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, Propyl pyruvate , N, N-dimethylformamide, dimethylmethylene maple, N-methylpyrrolidone, tetrahydrofuran, etc. are preferred, and these can be used alone or in combination. The chemically amplified positive photoresist composition of the present invention The object is coated on the substrate (such as silicon / silicon dioxide coating) used in the manufacture of precision electronic integrated circuits by a suitable coating method such as a spinner or a coater, -61-

-1— I ϋ I -------- · ——η- 装 ------ (Please read the precautions on the back before filling this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ^ 5645 A7 B7___ 1. Description of the invention (60) Exposure through a predetermined photomask, and baking and development, making a good Photoresist pattern. --Pack --- (Please read the precautions on the back before filling this page) The imaging solution of the chemically amplified positive photoresist composition of the present invention includes, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, silicon Inorganic bases such as sodium, sodium phosphate, sodium methyl silicate, ammonium water, primary amines such as ethylamine, n-propylamine, secondary amines such as diethylamine, di-n-butylamine, triethyl Tertiary amines such as amines, methyldiethylamine, alcohol amines such as dimethylethanolamine, triethanolamine, amines such as formamidine or acetamide, tetramethylammonium hydroxide, trimethyl (2- Hydroxyethyl) ammonium hydroxide, tetraethylammonium hydroxide, tributylmethylammonium hydroxide, tetraethanolammonium hydroxide, methylethanolammonium hydroxide, benzylmethyldiethanolammonium hydroxide, Tetraylammonium salts such as benzyldimethylethanolammonium hydroxide, benzyltriethanolammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and cyclic ammonium such as pyrrole and pyridine And other alkaline aqueous solutions. Lines [Examples] In the following, examples are synthesis examples, examples, and comparative examples, but the present invention is not limited by the following examples. Synthesis Example 1 [Synthesis of Copolymer (R-1)] Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 32.4 g (0.2 mol) of p-acetoxyphenylethyl hydrazone and 3.48 g (0.015 mol) of four Cyclic [6.2.1. 13,6.02, 7] dodecyl-4-acrylate was dissolved in 120 ml of butyl acetate, and 0.033 g of azobisisobutenenitrile was made at 80 ° C under stirring in a nitrogen gas stream. (AIBN) was added 3 times in 2.5 hours, and finally stirring was continued for another 5 hours to carry out the polymerization reaction. The reaction solution was poured into 1,200 ml of hexane, and a white resin was crystallized. Make the obtained resin-62- this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) which is 645 A7 B7 V. Description of the invention (61) i Pack --- (Please read the precautions on the back first Fill out this page again) After drying, dissolve 150 ml of methanol. An aqueous solution of 7.7 g (0.19 mol) of sodium hydroxide / 50 ml of water was added thereto, and the mixture was heated to reflux for 3 hours to hydrolyze. Then, it was diluted by adding 200 ml of water, and neutralized with hydrochloric acid to crystallize the white resin. The resin was filtered, washed with water, and dried. In addition, it was dissolved in 200 ml of tetrahydrofuran and vigorously stirred in 5 L of ultrapure water to perform dropping and reprecipitation. The reprecipitation operation was repeated 3 times. The obtained resin was dried in a vacuum dryer at 120 t for 12 hours to prepare a poly (p-hydroxystyrene / tetracyclododecyl acrylate) copolymer (R · 1). The weight average molecular weight of the obtained resin (polystyrene ring counted by GPC method) was 10,000. Synthesis Example a-2 [Synthesis of Copolymer (R-2)]-丨 In the Synthesis Example & -1, 4.632 (0.022 mol) bicyclic [4.4.0] decyl-3-acrylic acid was used instead of tetracyclic [6.2.1.13'6.02,7] Except dodecyl-4-acrylic acid, a (p-hydroxystyrene / bicyclodecyl acrylate) copolymer (R-2) was prepared in the same manner. The obtained resin had a weight average molecular weight of 12,000. Synthesis Examples a-3 to a-5 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, as in Synthesis Examples a -1 to a _ 2, the copolymer monomers and addition amounts were changed as shown in Table 1 to synthesize copolymers. . -63 · This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm) 495645 A7 __B7 V. Description of the invention (62) Table 1 Synthetic table of copolymers (R-1) to (R-5) 1 Synthetic example resin number polymer structure composition ratio x: y: z weight average molecular weight a — 1 R- 1 1 9 3: 7 1 0, 0 0 0 a — 2 R-2 Q ° CO 9 0:10 12,000 a — 3 R- 3 8 0:20 13,000 a — 4 R— 4 ^ & 8 5:15 1 1, 0 0 0 a — 5 R— 5 80:10:10 8,000 (Please read the precautions on the back before (Fill in this page) Printed Synthesis Example bl [Consumer of acid-decomposable polymer (B-1)] printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees' Cooperatives [20-g] Resin 20g (R-1) was dissolved in 100g propylene glycol methyl ether acetate In the ester (PGMEA), the solution was decompressed at 60 ° C and 20 mmHg, and about 20 g of the solvent was distilled off with water remaining in the system. Cool to 20 ° C, add 2.91 g (0.0291 mol) of 3-butyl vinyl ether and 0.05 g of p-toluenesulfonic acid pyridine-64- This paper is compliant with CNS A4 specification (210 X 297 public love) 5. Description of the invention (63) (Please read the precautions on the back before filling in this page) The solution of salt dissolved in 3.67g (0.0291 mole) of cyclohexanediol. After stirring was continued at 20 ° C for 2 hours, 0.04 g of triethylamine was added to stop the reaction. 100 ml of ethyl acetate was added to the reaction mixture, and 50 ml of water and 3 ml of 1 acetone were added for extraction. After repeating the water-washing extraction operation three times, the water in the distillation system was removed at 60 ° C and 20 mmHg. The concentration of this solution was adjusted to 20% with PGMEA (resin (B-1)). Synthesis Example b-2 [Synthesis of acid-decomposable polymer (B-2)] 20 g of resin (R-2) was dissolved in 100 g of PGMEA, and the solution was depressurized at 60 ° C and 20 mmHg, so that Approximately 20 g of the solvent was distilled off together with the water remaining in the system. After cooling to 20 ° C, 2.5 2 g (0.0349 mole) of vinyl vinyl ether and 0.05 g of p-toluenesulfonic acid pyridine salt were added. After stirring was continued at 20 ° C for 2 hours, 0.04 g of triethylamine was added to stop the reaction. 100 ml of ethyl acetate was added to the reaction mixture, and 50 ml of water and 3 ml of acetone were added to perform the extraction operation. After repeating the water washing extraction operation three times, the moisture in the unloading system at 60 ° C and 20 mmHg was removed. The concentration of this solution was adjusted to 20% with PGMEA (resin (B-2)). Synthesis Example b-3 [Synthesis of acid-decomposable polymer (B- 3)] Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs, dissolve 20g of resin (R-3) in 100g of PGMEA, and make the solution at 60 ° C The pressure was reduced at 20 mmHg, and about 20 g of the solvent was co-distilled off with the water remaining in the system. Cool to 2 (TC, add 5.93 g (0.023 3 mol) of 4-ethylene oxide ethyl-4- (3-butyl) cyclohexane pyridine salt. After stirring at 20 ° C for 2 hours, add 0.04g of triethylamine to stop the reaction. 100ml of ethyl acetate was added to the reaction mixture, and 50ml of water and 3ml of acetone were added to perform the extraction operation. After repeating the water washing extraction operation 3 times, it was removed at -65. Standard (CNS) A4 specification (210 X 297 mm) Milk 5645 A7 B7 I. Description of the invention (64) The water in the distillation system is distilled at 60 ° C and 20mmHg. The concentration of this solution is adjusted to 20% with PGMEA ( Resin (B-3)). -I · II (Please read the precautions on the back before filling this page) Synthesis Example b-4 [Synthesis of Acid Decomposable Polymer (B-4)] 20 g of resin (R- 4) Dissolve in 100g PGMEA, make the solution under reduced pressure at 60 ° C, 20mmHg, distill off about 20g of solvent and water remaining in the system. Cool to 20 ° C, add 3.84g (0.0383) Mol) A solution of 3-butyl vinyl ether and 0.05 g of p-toluenesulfonic acid pyridine dissolved in 4.14 g (0.0383 mol) of pentanol. Stirring is continued for 2 hours at 20 ° C. 0.04g of triethylamine was added to stop the reaction. 100ml of ethyl acetate was added to the reaction mixture, and 50ml of water and 3ml of acetone were added to perform the extraction operation. The washing operation was repeated 3 times, and the removal was performed at 60 ° C and 20mmHg. The water in the system was distilled off. The concentration of the solution was adjusted to 20% with PGMEA (resin (B-4)). Synthesis Example b-5 [Synthesis of Acid Decomposable Polymer (B-5)] | 20g of resin (R-5) was dissolved in 100g of PGMEA, the solution was depressurized at 60 ° C and 20mmHg, and about 20g of the solvent was distilled away with the water remaining in the system. Cool to 20 ° C, add 4.63g (0.0463 mol) Isobutyl vinyl ether and 0.05g p-toluenesulfonic acid pyridine salt are printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. After stirring for 2 hours at 20 ° C, 0.04g of triethylamine is added to Stop the reaction. Add 100 ml of ethyl acetate to the reaction mixture, and add 50 ml of water and 3 ml of acetone to perform the extraction operation. After repeating the water washing extraction operation 3 times, remove the water in the distillation system at 60 ° C and 20 mmHg. The concentration of this solution was adjusted to 20% with PGMEA (resin (B-5)). The list of acid-decomposable polymers is shown in Table 2. -66- This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) 495645 A7 B7 V. Description of the invention (65) Table 2 Acid-decomposable polymer

--- (Please read the precautions on the back before filling this page) 丨 Line _ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to make 20g poly (p-hydroxystyrene MVP- 8000 ·· made by Japan's Soda Co., Ltd.) It was dissolved in 100 g of propylene glycol methyl ether acetate (PGMEA), and the solution was depressurized at 60 ° C and 20 mmHg, and about 20 g of the solvent was distilled off with water remaining in the system. After cooling to 20 ° C, a solution of 4.17 g (0.0416 mol) of 3.butyl vinyl ether and 0.05 g of p-toluenesulfonic acid pyridine in 5.25 g (0.0416 mol) of cyclohexanediol was added. After stirring at 20 ° C for 2 hours, 0.04 g of triethylamine was added to stop the reaction. In the reaction mixture -67- This paper size is in accordance with Chinese National Standard (CNS) A4 specifications (210 X 297 public love 495645 A7 B7 V. Description of the invention (66) Add 100ml ethyl acetate, add 50ml water and 3ml acetone to carry out Extraction operation. After repeating the water washing extraction operation three times, the water in the distillation system was removed at 60 ° C and 20 mmHg. The concentration of this solution was adjusted to 20% resin ((C-1)) with PGMEA. Synthesis Example c -2 [Synthesis of acid-decomposable polymer (C-2)] 20 g of poly (p-hydroxystyrene MVP-8000: manufactured by Soda Co., Ltd.) was dissolved in 100 g of PGMEA, and the solution was dissolved in 60 g of Depressurize at 20 ° C and 20 mmHg to distill off about 20 g of solvent and water remaining in the system. Cool to 20 ° C, add 3.00 g (0.0416 mol) of ethyl vinyl ether and 0.05 g of p-toluenesulfonate. The acid pyridine salt was dissolved in 3.67 g (0.0291 mol). After stirring at 20 ° C for 2 hours, 0.04 g of triethylamine was added to stop the reaction. 100 ml of ethyl acetate was added to the reaction mixture, and another 50 ml was added. Water and 3m 1 of acetone for extraction operation. After repeating the water washing extraction operation 3 times, remove it at 60 ° C and 20mmHg. The water in the system was distilled off. The concentration of this solution was adjusted to 20% with PGMEA (resin (C-2)). Synthesis Example c-3 [Synthesis of Acid Decomposable Polymer (C-3)] 20 g (P-hydroxystyrene) (VP-8000: manufactured by Soda Co., Ltd.) was dissolved in 100 g of PGMEA, and the solution was depressurized at 6 (TC, 20 mmHg), and the solvent and the remainder were left in the system. The water was distilled off together. After cooling to 20 ° C, 8.47 g (0.0333 mol) of 2-ethylene oxide ethyl-4- (3-butyl) cyclohexanecarboxylate and 0.05 g of p-toluenesulfonic acid were added. Pyridine salt. After continuing to stir at 20 ° C for 2 hours, 0.04 g of triethylamine was added to stop the reaction. 100 ml of ethyl acetate was added to the reaction mixture, and 50 ml of water and 3 ml of acetone were added to perform the extraction operation. Repeated washing and extraction operations After 3 times, -68- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) -I-II (Please read the precautions on the back before filling this page) Order · · Line · Ministry of Economy Printed by the Intellectual Property Bureau's Consumer Cooperative ^ 5645 A7---- B7 V. Description of the invention (67) Remove the water in the system that is left at 60 ° C and 20mmHg The concentration of this solution was adjusted to 20% with PGMEA (resin (C-3)). (Please read the precautions on the back before filling out this page) Examples and Comparative Examples (Modulation and Evaluation of Radiation Sensitive Resin Compositions) Each raw material shown in Table 3 below was dissolved in 8 g of PGMEA, and filtered with a filter of 0.1 / 1 // n to prepare a resin composition solution (the PGMEA solution was used for each resin, and the table is expressed in terms of solid content conversion). ). The resin composition solution was uniformly coated on a silicon wafer treated with hexamethyldisilanes using a spin coater, and heated and dried at 120 ° C on a hot plate for 90 seconds to form 0. 5 // m barrier film. For this barrier film, a KrF excimer stepped exposure device (NA = 0.63) was used for pattern exposure using a line and gap mask, and after exposure, it was directly heated on a 11 (TC,, hot plate for 90 seconds. In addition, It was developed with a 2.3% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, washed with pure water in 30 seconds, and dried. Here, the obtained pattern was observed with a scanning electron microscope. The performance of the barrier is evaluated as follows. The sensitivity of the printed clothing of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is based on the smallest 0.24 // m line and space pattern on the reticle. The exposure energy (minimum exposure) is determined. The resolution is the critical resolution that can be resolved with this minimum exposure. The sidewall angle of the pattern is observed with a scanning electron microscope at a sidewall angle of the line pattern of 0.24 // m. The angle of the substrate surface is indicated. The forks in the lower part of the pattern are A without a fork, B with a slight fork, C with a significant fork, and D with an insert. -69- This paper standard applies to China National Standard (CNS) A4 Specification (210 X 297 mm) " 495645 A7 B7 V. Description of the invention (with) Table 3 Examples and Comparative Examples of Photoresist Compositions

No. Photoacid generator organic base compound Example 1 Bl (1.6g) D-3 (0.08g) E-3 (0.005g) 2 B-2 (1.6g) Dl (0.04g) D-2 ( 0.04g) El (0.005g) 3 B-3 (1.6g) D-3 (0.08g) E-2 (0.005g) 4 B-4 (1.6g) D-1 (0.09g) D-2 (0.08 g) E-3 (0.005g) l > I (0.l) l) 5g) — 5 B-5 (1.6g) 6 Bl (1.6g) D-3 (0.08g) E-2 (0.005g) 7 B-2 (1.6g) Dl (0.08g) E-3 (0.005g) 8 B-3 (1.6g) D-2 (0.08g) El (0.005g) 9 Bl (0.8g) B-2 ( 0.8g) D-3 (0.08g) E-2 (0.005g) Comparative Example 1 Cl (1.6g) D-3 (0.08g) E-3 (0.005g) 2 C-2 (1.6g) Dl (0.04 g) D-2 (0.04g) El (0.005g) 3 C-3 (1.6g) D-3 (0.08g) E-2 (0.005g) • I equipment-(Please read the precautions on the back first (Fill in this page)-丨 Line · Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-70- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 495645 A7 B7 Cooperative prints

(Please read the precautions on the back before filling in this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 495645 A7 ___B7 V. Description of the invention (70) Table 4 Examples and Comparative Examples No. Critical Resolution (// m) _Wall Angle (degrees) Bifurcation Case Example 1 0.17 88 A 2 0.18 88 A 3 0.17 89 A 4 0.17 88 A 5 0.18 89 A 6 0.17 88 A 7 0.18 88 A 8 0.18 88 A 9 0.17 89 A Comparative Example 1 0.21 86 C 2 0.22 86 D 3 0.21 85 ^ I — (Please read the precautions on the back before filling out this page) The Intellectual Property Bureau Employee Consumer Cooperatives of the Ministry of Economic Affairs printed as shown in Table 4 above It is shown that the resolution of the composition of the embodiment of the present invention, the perpendicularity of the side wall angle, and no bifurcation are all excellent. In addition, the 'comparative power of the composition of the comparative example is not good', especially the perpendicularity of the side wall angle and the bifurcation. [Effects of the Invention] According to the present invention, a chemically amplified positive photoresist composition having high resolution, excellent verticality of the sidewall angle of the pattern, and no branch at the bottom of the pattern can be obtained. 72- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

495645 (Amended on February 22, 1991) 6. Scope of patent application Λ scope of patent application: 1. A positive photoresist composition comprising: (a) at least the following general formulae (I), (II) and (III) Copolymer A of the constituent units shown in (I), (II), and (III) are 40 to 90 mole%, 5 to 40 mole%, and 3 to 40 mole%, respectively, (b ) Compounds which generate acid by active light or radiation, and (c) solvents; In the formulae (I) to (II), 1 and R2 each independently represent a hydrogen atom or a methyl group, and R4 represents a linear, branched, or cyclic alkyl group which may have a substituent, and an alkyl group which may have a substituent. Aryl, aryl which may have a substituent or a group represented by formula (IV), —γ—0—C * — ~ Z (IV) where Y represents a carbon number of 1 to 20 which may have a substituent , Z represents an alkyl group having 1 to 20 carbons which may have a substituent, a branched or cyclic alkyl group, an aryl group having 6 to 20 carbons which may have a substituent or an aralkyl group having 7 to 20 carbons which may have a substituent In formula (II I), 495645 6. Scope of patent application L represents a hydrogen atom or a methyl group, and X represents a saturated condensed polycyclic hydrocarbon which may have a substituent or a saturated bridged cyclic hydrocarbon which may have a substituent. 2. The positive photoresist composition according to item 1 of the scope of patent application, wherein (a) the copolymer (A) further contains a structural unit represented by the following general formula (V) ' (V) Among them, I is as defined in item 1 of the scope of the patent application, and R is hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, a methoxy group, or an ethoxy group. —