TW594414B - Positive photoresist composition - Google Patents

Abstract

Provided is a chemically amplified positive photoresist composition having excellent properties such as resolution, exposure margin, edge roughness of pattern, density dependency. A positive photoresist composition comprises (A) at least two photoacid generating agents which generate an acid upon irradiation with an active light or radiation and are selected from a sulfonate whose cationic portion consists of iodonium or sulfonium and whose anionic portion consists of anion represented by RFSO3 wherein RF represents a fluorine-substituted alkyl group having 1 to 20 carbon atoms and the difference in carbon number of the anionic portion is in the range of 2 to 15, and (B) a resin whose solubility in an alkali developing solution is increased by the action of an acid and has repeating unit of specific structure.

Description

594414 V. Description of the Invention (1) Technical Field The present invention relates to a positive photoresist composition for use in ultralithography process or other photoresist application process for manufacturing ultra-LSI or high-capacity microchip. More specifically, the present invention relates to a positive-type photoresist composition for far-ultraviolet exposure using a far-ultraviolet range containing an excimer laser light, particularly a wavelength of less than 250 nm, to form a high-definition image. Prior art In recent years, in order to further increase the integration degree of integrated circuits, ultra-fine images made of line widths of less than half a micrometer must be processed in semiconductor substrates such as super LSIs. To meet this need, the wavelength used by the exposure device used in lithography is made shorter, and far-ultraviolet light or excimer laser light (XeCl, KrF, ArF, etc.) is also currently being reviewed. When the lithographic resin image of this wavelength range is formed, the user is a chemically amplified photoresist. It is proposed to introduce a resin for an alicyclic hydrocarbon site for the purpose of imparting dry etching resistance to a photoresist composition for an ArF light source. This resin is, for example, a resin having a monomer having a carboxylic acid moiety of acrylic acid or (meth) acrylic acid, or a monomer having a hydroxyl group or a cyano group in the molecule, and a monomer having an alicyclic hydrocarbon group. In addition to the above-mentioned method of introducing an alicyclic hydrocarbon site into the side chain of an acrylate monomer, the method of making the alicyclic hydrocarbon site of the polymer main chain active against dry etching has also been reviewed. In addition, Japanese Unexamined Patent Publication No. 9-73173, Japanese Unexamined Patent Publication No. 9-90637, and Japanese Unexamined Patent Publication No. 10-161313 describe the use of a compound containing an alicyclic structure.

594414 V. Description of the invention (2 :) A protective photoresist material is formed by dissolving a protective soluble group and dissolving the base soluble group with an acid to form an alkali-soluble structure. In addition, it has been described in JP 9-90637, JP 10-207069, and JP 10-274852, JP 10-239846, which are introduced into these resins having an alicyclic group to improve the performance of alkali developing solutions. A resin with a large 5-carbon ring or 6-carbon lactone group with affinity or adhesion to the substrate. In the above-mentioned techniques1 there is still a need for improvement caused by acid-decomposable resins in photoresist compositions (especially photoresists for far-ultraviolet exposure). Point I 0 However, these compositions have rough edges due to line patterns. Factors such as sex have problems that hinder pattern resolution. Here, the line edge roughness refers to the irregularity of the line direction and the vertical direction caused by the photoresist characteristics at the edges of the top and bottom edges of the line pattern of the photoresist. Questions about the relevance of density need to be improved. The tendency of the most recent devices is to include various patterns in order to obtain various properties in the photoresist. One of them is the density-related property. In other words, the part of the device that has a dense set of wires, that is, a pattern with a wide gap when compared with a wire, and an isolated wire. Therefore, it is extremely important that the various wires have local reproducibility to be resolved. However, there are no cases where the various line reproduction systems are easier than optical factors, and the solution method of photoresist is not clear. Especially in the above alicyclic group-based photoresist system, the performance difference between isolated patterns and dense patterns is significant, and it is sought to improve 0. Moreover, the conventional photoresist composition has exposure correlation related to pattern line width changes due to subtle changes in exposure. Sexual problems, -4-

594414 V. Description of the invention (3) Photoresist composition with wide exposure range. Therefore, an object of the present invention is to provide a chemically amplified positive photoresist composition which is excellent in resolution, exposure range, edge roughness of a pattern, and denseness. The invention shows that the present inventors have repeatedly studied the constituent materials of the positive type chemical amplification photoresist composition, and found that the use of a resin having a specific photoacid generator and lactone structure can achieve the purpose of the present invention. Then, the present invention is completed. In other words, the above-mentioned object can be achieved by the following constitution. (1) A positive photoresist composition, characterized in that (A) is selected from the group consisting of a cationic moiety consisting of iodine or fluorene and an anion moiety consisting of RFs0r (wherein RF is fluorine having 1 to 20 carbon atoms Sulfonate composed of anion shown by substituted alkyl), and the difference in carbon number of RF between at least two anion parts is 2 to 15. 5. A photoacid generator that generates an acid by active light or radiation, (B) contains A resin having at least one repeating unit represented by the following general formulae (1-1) to (1-4) and decomposed by an acid to increase solubility in alkali,

(1-1) (Bu 2) 594414 V. Description of the invention (4) R1 r2

(Bu 4) (where 'R! ~ R5 represents the same or different, hydrogen atom, optionally substituted alkyl, cycloalkyl or alkenyl, 2 of 1 ^ ~ 卩 5 can be bonded to form a ring) . (2) The positive photoresist composition according to the above (1), wherein (a) the photoacid generator having a relatively large carbon number in the component RF is selected from the anion portion and the RF is 4 to 20 linear carbons A photo-acid generator having a fluorine-substituted alkyl group and a relatively small carbon number of RF is selected from a linear substituted alkyl photo-acid generator having 1 to 5 carbons of RF in the anion portion. (3) The positive-type photoresist composition according to (1) or (2) above, wherein at least one photoacid generator is represented by the following formula (I), (II), or (III).

⑴

594414

V. Description of the invention (5)

, Branched or cyclic alkyl, straight chain, branched or cyclic alkoxy, hydroxyl, halogen atom, or-s-r38, R38 represents straight chain, branched or cyclic courtyard Or aryl, and Ri ~ Ri5, R16 ~ R27, or R28 ~ R37 may be bonded by two or more to form a ring containing one or two or more kinds selected from single bond, carbon, oxygen, sulfur, and nitrogen) (4 ) The positive photoresist composition according to the above (1) to (3), wherein (B) the resin further contains an alicyclic hydrocarbon represented by at least one of the following general formulae (pl) to (PVI) A repeating unit of an alkali-soluble group protected by a structural base. 594414 V. Description of the invention (6 «11 ㈣ (pH)

R 14

R1 OlCH

(PI R—c—R ^

.6 Ό R1R20

I 21 23 R— 22. R—

H c- ^ C——R 24 R-one

I 〇- on c R, wp- \, '丨 z. (Wherein, Rn represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or 2-butyl, Z Is a carbon atom and an atomic group necessary to form a cyclic hydrocarbon group, 594414 V. Description of the invention (7) R12 ~ Ru series each represent an independent carbon number of 1 to 4 straight or branched chain or alicyclic hydrocarbon groups, At least one of R12 to R14, and any of R15 and R16 is an alicyclic hydrocarbon group. R17 to R21 each represent a hydrogen atom and a carbon chain of 1 to 4 linear or branched alkyl or alicyclic hydrocarbon groups. R17 to R14 At least one of R21 is an alicyclic hydrocarbon group, and either of R19 and R21 is a linear or branched alkyl or alicyclic hydrocarbon group having 1 to 4 carbon atoms, and R22 to R25 each represent an independent carbon number of 1 to 4 A linear or branched alkyl group or an alicyclic hydrocarbon group, at least one of R22 to R25 is an alicyclic hydrocarbon group, and r23 and r24 may be bonded to each other to form a ring). (5) The positive photoresist composition according to the above (1) to (4), wherein the base system containing the alicyclic hydrocarbon structure represented by the general formula (Pi) to the general formula (pVI) is the following general formula ( pla).

(R3〇) q (wherein R28 represents an alkyl group which may have a substituent, and R29 to r31 represent the same or different hydroxyl, halogen atom, carboxyl group, or an alkyl group, a cycloalkyl group, or an alkenyl group which may have a substituent , Alkoxy, alkoxycarbonyl or fluorenyl, each of P, q, and r represents an independent integer of 0 or 1 to 3). (6) The positive photoresist composition according to the above (1) to (5), in which (B) a resin 594414

5. Description of the Invention (8) The system contains a repeating unit represented by the following general formula (a). R 〇

(Wherein R represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 4 to 4 carbon atoms, R32 to R34 represent the same or different hydrogen atoms or hydroxyl groups, and at least one of R32 to R34 is Hydroxyl). In addition, the following form is preferable. (7) The positive-type photoresist composition according to the above (1) to (6), further comprising (C) an acid diffusion inhibitor. Embodiments of the Invention The compounds used in the present invention will be described in detail below. < (A) A compound that generates an acid by active light or radiation (referred to as a photoacid generator or (A) component) > The photoacid generator of the present invention uses at least two kinds of cationic moieties to iodine key or spread. The composition and anion are selected from the photoacid generators shown in RFS03- (wherein RF is a fluorine-substituted alkyl group having 1 to 20 carbon atoms) and the number of anion portions differs from 2 to 15.

-10- 594414

594414 V. Description of the invention (10) Branched or cyclic alkyl group, straight chain, branched or cyclic alkoxy group, hydroxyl group, halogen atom, or _S-R38, R38 means straight chain, Branched or cyclic courtyard or aryl group, and Ri ~ R15, R16 ~ R27, or R28 ~ R37 may be bonded by two or more kinds. It contains one or more kinds selected from single bond, carbon, oxygen, and sulfur. And the ring of nitrogen) The present invention is a sulfonate composed of an anion selected from RFS03 · (where RF represents a fluorine-substituted alkyl group having a carbon number of 1 to 20) using a cationic moiety composed of iodine or hydrazone or an anion. Of several photoacid generators. The fluorine-substituted alkyl group represented by RF may be any of linear, branched, and cyclic. A preferred RF is a straight-chain alkyl substituted with fluorine represented by CF3 (CF2) y and y is an integer of 0 to 9. -S-, -CO-, -COO-, _NHCO-, -C0NHS02- and the like are bivalent bond groups. In addition, the carbon number of R7 at this time is a carbon number containing a bonding group. In addition, the alkyl group represented by RF may be substituted by one or more fluorine atoms, and a hydrogen atom of a carbon atom at the α-position of a sulfonic acid is preferably substituted with a fluorine atom. The composition of the present invention contains at least two (one pair) of the above-mentioned photoacid generators having a carbon number difference of 2 to 15, preferably 3 to 7, as the photoacid generator. For example, when using three types of photoacid generators with carbon numbers of 3, 4, and 5, respectively, the above conditions for the existence of a pair of photoacid generators with a carbon number difference of 2 to 15 in RF are satisfied. In addition, when three kinds of photoacid generators each having a carbon number of 2, 6, 8, or the like are used, the above-mentioned conditions in which there are three pairs are satisfied. The total amount of the photoacid generator in the above-mentioned photoacid generator containing at least two kinds is preferably 50 to 100 mole% for all photoacid generators. -12-594414 V. Description of the invention (11) More preferably, it is 70 to 100 mole%. The positive-type photoresist composition of the present invention contains a plurality of photoacid generators satisfying the above-mentioned conditions, specifically, the following (B) specific resin (B-.1) or polymer (B-2) 'may It is obtained by those who have excellent characteristics such as resolution, exposure range, pattern edge roughness, and dense correlation in the lithography application method using ArF excimer light. In a preferred embodiment, among the photoacid generators in which the carbon number difference of rf of at least one pair of anion parts is 2 to 15, the RF system in the photoacid generator having a relatively large carbon number in RF is 4 to carbon. 20 straight-chain fluorine-substituted alkyl (hereinafter referred to as "photoacid generator A1"), and the RF system of the relatively small RF carbon number of the photoacid generator is 1 to 5 carbon linear Fluorine-substituted alkyl group (hereinafter referred to as "photoacid generator A2"). The molar ratio (A1 / A2) of the photoacid generator A1 to the photoacid generator A2 is 90/10 to 10/90, and more preferably 80/20 to 20/80. The cationic part of the photoacid generator is preferably represented by the general formulae (I) to (III) above. In the general formulae (I) to (III), 1 to: ^ 8 linear or branched alkyl groups For example, a methyl group, an ethyl group, a propyl group, an isobutyl group, a 2-butyl group, and a 3-butyl group having a substituent have 1 to 4 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group having 3 to 8 carbon atoms which may have a substituent. Examples of linear and branched alkoxy groups of Ri to R37 include methoxy, ethoxy, hydroxyethoxy, propoxy, n-butoxy, isobutoxy, 2-butoxy, Those having a carbon number of 1 to 4 such as a 3-butoxy group. -13- 594414 V. Description of the Invention (彳 2) The cyclic alkoxy group is a cyclopentyloxy group, for example, a cyclopentyloxy group, a cyclohexyloxy group, and a halogen atom of a core group such as a fluorine atom and a chlorine atom , Bromine atom, bowl atom, etc. Examples of the aryl group of Rn include phenyl, tolyl, methoxyphenyl, and naphthyl having 6 to 14 carbon atoms which may have a substituent. The substituents of this temple are 1 to 4 carbon atoms, halogen atoms (fluorine atom, chlorine atom, mill atom), 6 to 10 carbon atoms, 2 to 6 carbon atoms, cyano, Hydroxyl, carboxyl, carboxycarbonyl, nitro and the like. In addition, '1 ^ ~ 1 {15, R16 ~ R27, or R28 ~ R37 may form two or more bonds to form a ring containing one or two or more kinds selected from single bonds, carbon, oxygen, sulfur, and nitrogen. For example, there is a furan ring. , Dihydrofuran ring, pyran ring, trihydropyran ring, thiophene ring, pyrrole ring and the like. A photoacid generator represented by the following general formula (IV) or (V) is preferred. Compounds having an acid and a benzamidinemethylsulfonium salt structure generated by active light or radiation irradiation are, for example, compounds represented by the following general formula (IV).

Among them, 'Rle ~ is a gas atom, a carbyl group, a carboxy group, or a halogen atom, each of which does not represent AL alone. -14- 594414 V. Description of the invention (13) ~ R7. Each represents an independent hydrogen atom, an alkyl group, or an aryl group. Rx and Ry each independently represent an alkyl group, a 2-carbonylalkyl group, an alkoxycarbonylmethyl group, an aryl group, or a vinyl group. Any two or more of Rlc to R7e and Rx are bonded to form a ring structure, and the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, and a amide bond. X · stands for RfS03_. RF is the same as the above. Rlc ~ R5. The alkyl group may be linear, branched, or cyclic, for example, an alkyl group having 1 to 10 carbon atoms, preferably a linear or branched alkyl group having 1 to 5 carbon atoms (eg, methyl, ethyl, straight Chain or branched propyl, straight or branched butyl, straight or branched pentyl), cyclic alkyl with 3 to 8 carbons (eg cyclopentyl, cyclohexyl)

Rlc ~ R5. The alkoxy group may be linear, branched, or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear and branched alkoxy group having 1 to 5 carbon atoms (for example, methoxy, Ethoxy, straight or branched chain propoxy, straight or branched chain butoxy, straight or branched chain pentyloxy), cyclic alkoxy groups with 3 to 8 carbon atoms (such as cyclopentyloxy, Cyclohexyloxy). The preferred Rle ~ R5. It is a straight chain, branched chain, cyclic alkyl group, or straight chain, branched chain, or cyclic alkoxy group, and more preferably, the sum of carbon numbers of Ru to R5e is 2 to 15. Thereby, the solubility of a solvent can be further improved, and generation of particles during storage can be controlled. About R6e and R7. The alkyl system is related to Ri. ~ R5. The same alkyl group. Aryl is, for example, an aryl having 6 to 14 carbon atoms (for example, phenyl). The alkyl groups of Rx and Ry are Ru to R5. The same alkyl group. 2-Several bases are based in Ri. ~ R5 (: The 2nd place of the courtyard base has> C = 0

-15- 594414 V. The basis of invention description (14). The alkoxy group of alkoxycarbonylmethyl is Ru ~ R5. The alkoxy groups are the same. Rx and Ry are bonded to form a ring such as butenyl, pentenyl, and the like. The compound of formula (IV) can form a ring to fix the three-dimensional structure and improve the photodecomposition energy. h. ~ R7. When any two of these bonds form a ring structure, Rl. ~] ^. Either with R6. And R7. Any one of them is preferably a single or double bond to form a ring, and more preferably R5. With R6. Or R7. Bonded to form a single or double bond to form a ring-bonding group such as an alkylene group which may have a substituent, an alkenyl group which may have a substituent, -0-, -S-, -CO-, -CONR- (R means A hydrogen atom, an alkyl group, a fluorenyl group), and a group formed by combining two or more of these. Further, an alkylene group which may have a substituent, an oxygen-containing alkylene group, and a sulfur-containing alkylene group are preferred. Examples of the substituent include a fluorenyl group (preferably having 1 to 5 carbons), an aryl group (preferably having 6 to 10 carbons, such as phenyl), and a fluorenyl group (eg, 2 to 1 1 carbons). In addition, a methyl group, an ethyl group, an propyl group, -CH2-0-, and -CH2-S- are preferred to form a 5 to 7 carbocyclic bond group, and the more preferred group is an ethyl group, -CH2 -0-, -CH2-S_ which forms a 6-carbon ring bonding group. By forming a 6-carbon ring, the carbonyl plane and the C-S + 5 bond can be made closer to perpendicular, and the photodecomposition energy can be improved by orbital interaction. Alternatively, it may be from RU to R7. And compounds in which Rx and Ry are bonded via a single bond or a double bond at any position and have two or more structures of formula (IV). The salt system without aromatic ring is represented by the following formula (V)

-16- 594414 V. Description of the Invention (is) Salt.

(Among them, Rlb ~ R3b each represents an independent organic group without an aromatic ring, and the aromatic ring here also includes a hetero atom-containing aromatic ring, and XI represents RFS < V, and RF is the same as above) Rlb The organic group not containing an aromatic ring to R3b is generally 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms. Rlb to R3b each independently represent an alkyl group, a 2-carbonylalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group, and more preferably a linear, branched, or cyclic 2-carbonylalkane And alkoxycarbonylmethyl, linear and branched 2-carbonylalkyl are preferred. The alkyl group of Rlb ~ R3b may be linear, branched, or cyclic, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, propyl, butyl, and pentyl) ), A cyclic alkyl group (cyclopentyl, cyclohexyl, orthospinyl) having 3 to 10 carbon atoms. The 2-carbonylalkyl group of Rlb to R3b may be linear, branched, or cyclic, and is preferably, for example, h. The alkyl group of ~ R5e has a group of > C = 0 at the 2-position. As the alkoxycarbonylmethyl group of Rlb to R3b, for example, a linear or branched alkyl group having 1 to 5 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl) is preferred. Rlb ~ R3b may be substituted with a halogen atom, an alkoxy group (for example, a carbon number of 1 to 5), a hydroxyl group of -17-594414, or a cyano group or a nitro group. In Rib ~, two bonds can be formed to form a ring structure. The ring may also contain an oxygen atom, a sulfur atom, an ester bond, an amidine bond, and a carbonyl group. Examples of the groups formed by the two bonds in Rlb ~ R3b are, for example, alkylene (e.g., butylene and pentayl). In terms of photoreactivity, it is preferable that at least one Rlb to R3b is a group having a carbon-carbon double bond or a carbon-oxygen double bond. At least one Rlb to R3b of the compound represented by the general formula (V) may have a structure bonded to at least one Rlb to R3b of the other compounds represented by the general formula (V). Specific examples (A1-1) to (A1 -91) of the photoacid generator A1 usable in the present invention are shown below.

-18- 594414

594414 V. Description of the invention (18 t-Bu

CF3 (CF2) 3S〇J

CF3 (CF2) 7S〇3 t-Bu

Or (A1H3)

Or (A1 -14)

h3co

Cl

(A1-17)

Cl

h3co

s; CF3 (CF2) 9S〇3

(A1-20) -20- 594414

594414 V. Description of Invention (20)

HO

(Α1-29), ~ ^ Γ

(A1-32) H3C0H0 ^ S (_CF3 (CF2) 7S0 ^ Η3〇0 ^ 0 ^

S 2 CF3 (CF2) 3S〇3 一 (A1-33)

• S 2 CF3 (CF2) 5S〇3 (AV34)

S 2 CF3 {CF2) 7S〇3 (A1-35) -22- 594414 V. Description of the invention (21)

s

• S 乂 2 CF3 (CF2) 9S〇; (A1-36)

S

_S 2 CF3 (CF2) 3S〇3 一 (A1-37>

S

• S 2 CF3 (CF2) 7S03 " (A1-38)

Cl

S 2 CF3 (CF2) 3S03-

-23- 594414

594414 V. Description of the invention (23)

O (CH2) 20H

CF 3 (CF 2) 3 ^ 03 (A1-45) _S 2 CF3 (CF2) 7S〇3- General CF3 (CF2) 5S〇 ;. _: ·. (A1-46) Deadlock: ◎ CF3 (CF2 ) 7S〇3 (Α1-47) l + CF3 (CF2) 3SOJ (A1-49)

(A1-50)

J—rCF3 (CF2) 7SOJ (A1-51) l + CF3 (CF2) 3S〇3 (A1-53) 1 + cf3 (cf2) 9so;

(A1-52) • | + CF3 (CF2) 7S〇3 (A1-54) < Q >-| 1- < Q)-〇--c5h17 cf3 (cf2) 3so ~ 3 (A1-55) CF3 (CF2) 7S〇3 (A1-56) -25- 594414 V. Description of the invention (24

(A1-58)

Me〇1 J 十 Γ CF3 (CF2) 3SO; Ren Guang CF3 (CF?) 7SO; (A1-57): ι ^ -ι cl ^ U ^ r CF3 (CF2) 3SO; (A1-59) *

Cl

I CF3 (CF2) 7S〇3 (A1-50)

I! NHCOC 8H17 CF3 (CF2) 9S〇] (A1 t64) -26- 594414 5. Description of the invention (25

CF3 (CF 2) 3 ^^ 3- (A1-65)

CF3 (CF2) 7S〇3- (A1-66)

CF3 (CF2) 7S〇3_ (A1-69) cf3cf2-o-cf2cf2so3- (A1-67)

〇5sQ CF3 (CF 2) 3 ^^ 3- (A1-71) CF3 (CF2) 7S03- (A1-72) 〇5 s〇

CF3 (CF2) 3S03 (A1-74) CF3CF2-0-CF2CF2S〇3- (A1-73) -27- 594414

594414 V. Description of the invention (27) CF3 (CF2) 3S〇3 * · CF3 (CF2> 7S〇3- (A1-86) (A1-87) G 丄 cf3cf2-o-cf2cf2so3- cf3 (cf2) 3so3- ( A1-B8) (A1-89) '. -... **. G. CF3 (CF2) 7S〇3- CF3CF2-0-CF2CF2S〇3- (A1-90) (A1-91): This Specific examples (A2-1) of the photoacid generator A2 usable in the invention (A2-1) 7 4) are shown below. ~ (A2--29-594414 V. Description of the invention (28

(Or S CF3SOJ (A2-1) s + CF3 (CF2) 2so; (A2-3)

CF3CF2S〇3 (A2-2) S + CF3 (CF2) 3SOJ (A2-4)

, (A2-7) 〇

cr

s cf3cf2s〇3 (A2-6)

S + CF3 (CF2) 3S〇3 s

cf3so3a 3 (A2-8) Cl

o ~

Cl (A2-9) t-Bu

(A2-11) t-Bu

(A2 -12) -30- 594414

594414 V. Description of Invention (30)

cF3S〇3 · b (A2-23>

< Qh-s-hQ > -s / + CF3 (CF2) 3S〇3b (A2-24) CF3SO3 CF3 (CF2) 3S〇3 (A2-25) (A2-26)

, S 2 CF3SO3 " · 2 (A2-27)

S 2 CF3CF2SO3 (A2-· 28) -32- 594414 V. Description of the invention (31 ύ

• S 2 CF3 (CF2) 2S〇3 2 (A2-29)

-S 2 CF3 (CF2) 3S〇3

s

-s 2 CF3SO3

_S 2 CF3 (CF2) 3S〇3 -33- 594414 V. Description of the invention (32)

S 2 CF3SO3 * "-

S 2 CF3CF2SO3 " · S 2 CF3SO3 CI-

S 2 CF3 (CF2) 3S03- (A2-36)

-34- 594414 V. Description of the Invention (33) o (ch2) 2oh

S 2 CF3SD3

0 (CH2) 20H

CF3S03 s 2 CF3 (CF2) 3SOf General (A2-39) General

CF3SO3 " CF3 (CF2) 2S〇3 (A2-41)

(A2-44) (A2-43)

+ *) — I CF3 (CF2) 2SOJ (A2-45)

i + cf3 (cf2) 3so] (A2-46) -35- 594414 V. Description of the invention (34)

I CF3SO3- (A2-47)

Cp3 (CF2) 3S〇3 (A2-4B) 'λ CF3SO3 (A2-49) -c8h17' cf3so3: (person 2 50)

(A2-53)

MeO

Cl

I CF3 (CF2) 3S〇3 2 (A2-52) CF3 (0F2) 3S〇3 I.: ·; (A2-54) Cp3 (CF2) 3S〇3 (A2 ~ 56): · < 0 > — | ^-< 〇 >-hidden 〇. Office 7 CF3 (CF2) 3SCT3 (A2-57) NHC〇C8H17 CF3 (CF2) 3S〇3 (A2-5B)

-36- 594414

594414 V. Description of the invention (36) CF3S03-0 (A2-70) Cs ^ X ^ CF3SO3- (A2-72) CF3SO3- (A2-74) Moreover, the photoacid generator A1 generates CF3 (CF2) 3S03H, CF3 The compound of (CF2) 7S03H is preferred, and the compound of photoacid generator A2 to generate CF3S03H, CF3 (CF2) 3S03H is preferred. The preferred combination of photoacid generators A1 and A2 (photoacid generators A1 / A2 and acid generation) is CF3 (CF2) 3S03H / CF3S03H, CF3 (CF2) S03H / CF3S03H, cf3 (cf2) 7so3h / cf3 ( cf2) 3so3h. The additive of the photoacid generator of the component (A) in the present invention, that is, the total amount of two or more photoacid generators is generally 0.001 to 40% by weight based on the solid content of the composition, preferably 0.01 ~ 20% by weight, more preferably 0.1 to 5% by weight. If the added amount of the photoacid generator is less than 0.001 wt%, the sensitivity is low, and if it is more than 40 wt%, the light absorption of the photoresist is too high.

0 CF3 (CF2) 3S〇3- (A2-69) CF3 (CF2) 3S〇3- (A2-71) CF3 (CF2) 3 ^^ 3 ^ (A2-73) -38- 594414 V. Description of the invention ( 37) Deterioration of appearance and narrow scope of engineering (especially baking) are not desirable. The photoacid generator A1 or the salt of the photoacid generator A2 can be reacted with, for example, an aryl Grignard reagent such as an aryl magnesium bromide and a substituted or unsubstituted phenylene group to react the obtained triarylsulfonium A method for exchanging a methyl halide with a corresponding sulfonate, or condensing a substituted or unsubstituted phenylene with a corresponding aromatic compound using an acid catalyst such as methanesulfonic acid / pentaoxophosphate or aluminum chloride The method of salt exchange is synthesized by using a diaryl iodonium salt and a diaryl sulfonate to condense using a catalyst such as ketone acetate, or a salt exchange method. In addition, the iodonium salt of the photoacid generator A1 or the photoacid generator A2 can be synthesized by reacting an aromatic compound with a periodate, and subjecting the obtained iron iodide salt to a corresponding sulfonate for salt exchange. The sulfonic acid or sulfonate used in the salt exchange can be obtained by directly using a commercially available sulfonic acid or hydrolyzing a sulfonic acid halide. In the positive-type photoresist composition of the present invention, a photoacid generator other than the specific compound described above may be used. As the photoacid generator that can be used, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photochromic agent for pigments, a photochromic agent, or a microphotoresist can be used. Conventional light (400 ~ 200nm ultraviolet, 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 These mixtures are appropriately selected. In addition, other photoacid generators used in the present invention include diazo iron salts,

-39- 594414 V. Description of the invention (38) Ammonium salt, scale salt, iodonium salt, selenium salt, selenium salt, arsenic salt, organic halogen compound, organic metal / organic halide, ortho-nitrobenzene Basic photoprotective groups such as photo-generating agents, iminosulfonates, and other typical photodecomposition compounds that generate sulfonic acids, dihydrazone compounds, diazonium hydrazones, and diazodifluorene compounds. In addition, these can be used by A compound that generates an acid group by light or introduces a compound into the main or side chain of a polymer. Alternatively, VNRPillai, Synthesis, (1), 1 (1980), A. Ab ad 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. 1,26,7 1 2 are compounds which generate acid by light. Among the compounds which generate acid by irradiation with active light or radiation and decompose, particularly effective users are compounds represented by the following general formula (PAG3), general formula (PAG4), general formula (PAG6) or general formula (PAG7). Shoot 1 \ " Z At2 (PAG3) R ^ 3 R2〇4 \ seze R205 (PAG4)

R

9 n2〇 ^ RS— ^ S—R ”II 〇〇 (PAG7) 40- 594414 V. Description of the invention (39) In the general formulae (PAG3) and (PAG4), Ar1 and Ar2 represent each independently substituted Or unsubstituted aryl groups. Preferred substituents are, for example, alkyl, haloalkyl, cycloalkyl, aryl, alkoxy, nitro, endyl, alkoxycarbonyl, hydroxyl, fluorenyl, and halogen. Atoms: R2 03, R 2 04, and R 2 05 each represent an independently substituted or unsubstituted alkyl group or aryl group. Preferred are aryl groups having 6 to 14 carbon atoms and 1 to 8 carbon atoms. And substituted derivatives thereof. Preferred substituents for the aryl group include a carboxyl group having 1 to 8 carbon atoms, a carboxyl group having 1 to 8 carbon atoms, a nitro group, an end group, a warp group, and a halogen atom. For alkyl groups, there are alkoxy groups, residues, and oxycarbonyl groups having 1 to 8 carbon atoms. Z · represents a counter anion, such as BF4 ·, AsF6 ·, ρρ6 ·, sbf, si F6 _, c 1 〇4 _, sulfonic acid that can be substituted, perfluorinated sulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, anthracenesulfonic acid that can be substituted, but the present invention is not limited by these. The preferred is alkanesulfonic acid Acid, perfluoroalkanesulfonic acid, alkyl substitution Benzoic acid and pentafluorobenzenesulfonic acid. In addition, at least two of r2G3, r204, and r205, and Ari and Ar2 may each be a single bond or bonded through a substituent. General formula (PAG6), (PAG7) "R2Q6" is a substituted or unsubstituted alkyl group or aryl group. "A" means a substituted or unsubstituted alkylene group, a vinyl group, or an arylene group. "R" means a linear branched or cyclic alkane Group, or substituted or unsubstituted aryl group. Specific examples include the compounds shown below, but are not limited by these. -41-594414 V. Description of the Invention (40)

-42- 594414 V. Description of the invention (41 〇 〇 OBu

N—O — SO. · ’N n ~ o-so2-cf3

N_O_S02_CF3 N_0_S〇2 ~; 〇 (PAG6-2) 〇

〇 (PAG6-3) 〇 w. O

〇O o ~ (PA67-1) (PAG7-2) (PAG7-3) s— ^ s- 〇o $! Ί 2 9 (PAG7-4) (PAG7-5) In the present invention, Among the photoacid generators, those represented by the general formula (PAG7) are preferable. -43- 594414 V. Description of the Invention (42) These photoacid generators are used based on the solid content of the composition as a basis of 5% by weight or less, preferably 2% by weight or less. < (B) Resin which decomposes by acid action and increases solubility in alkali > The above-mentioned (B) resin used in the composition of the present invention, which decomposes by acid action and increases solubility in alkali ( Hereinafter referred to as "the resin of (B)"), it includes a repeating unit having a group represented by the general formulae (1-1) to (1-4). In the general formulae (1-1) to (1-4), the alkyl group of ^ ~: ^ is, for example, a linear or branched alkyl group, and may have a substituent. The linear or branched alkyl group is preferably 1 to 12 carbon or linear or branched alkyl groups, and more preferably 1 to 10 linear or branched alkyl groups. Preferred are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl, pentyl, hexyl, heptyl, octyl, nonyl, Decyl. heart~! The cycloalkyl group is preferably a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like having 3 to 8 carbon atoms. The alkenyl group is preferably a carbon number of 2 to 6 such as vinyl, propenyl, butenyl, and hexenyl. In addition, two of h to R5 are bonded to form a ring such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cyclooctane ring and the like. Furthermore, M to R5 in the general formulae (1-1) and (1-2) may be bonded to any one of the seven carbon numbers constituting the ring structure. In addition, the other substituents of the above-mentioned alkyl group, cycloalkyl group, and alkenyl group are, for example, alkoxy groups having 1 to 4 carbon atoms, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), fluorenyl group, fluorenyl group, Cyanyl, hydroxyl, carboxyl, alkoxycarbonyl-44-594414 5. Description of the invention (43), nitro. The repeating unit having a group represented by the general formulae (1-1) to (1-4) is preferably a repeating unit represented by the following general formula (AI).

However, R is synonymous with R in the following general formula (a). A 'represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group combining these. B is a group represented by any one of the general formulae (I-1) to (I-4). The divalent base of the combination in A 'is, for example, the following,

-45- 594414 V. Description of the invention (44

Os? -〇—ch2ch2—c ^ -o—ί-c

Rb / Π • CH2CH2 ~ Ο-Ό-OH2CH2 一 c— 〇 〇 〇

Rb / η wherein Ra, Rb, and r 1 are each synonymous with the following. M is an integer of 1 to 3. In the following, specific examples of the repeating unit represented by the general formula (AI) are shown, but the content of the present invention is not limited by these. -46- 594414 V. Description of the invention (45

CH 3 ch3 ch2-c · ten h2- c- C-0 0 0

(Μ) 〇

ch3 ten h2-c ^-

(1-3)

-icH2-CH; CH2 — CH · c —0 Ο

(1-5) 〇

(Bu 6) * CH, C-0 〇

(1-7)

-47- 594414 V. Description of the invention (46)-(ch2- (ch3 ^ ch2—〇4-

(1-9)

— ^ CH2_Chl · • CH2-CH · c-o 〇

o c one o 〇 / h3c h3c b

(1-11) (M2)

-48- 594414 V. Description of the invention (47 CH〇— (* CH2— < 〇 々 c-〇 〇 .C-Q 〇, // 々 一 C \ H ^ c U 0 h3c (1-17)

rf \ ^ CH3 /?-cx H3C0h3 〇 · 〇 (1-18)

O CH3 ch3-(ch2-c_ 一 (》 ch2-c · See c-o o (ch2) 2-ct o 〇 e-o (M9)

(ch2) 2-cn 〇 Wide ch3 〇

ch3-| ch2-c-

ο (I-20) CH3-fCH2-〇V 〇 c-〇 〇 // (CH2) 2-c, 〇 · H3c- (1-21) 〇

C ~ O 〇 pu 々 N // VH3 〇 (CH2) 2-C, 〇 (I-22)

〇ch3 ^ CH2 ~ c- c_〇〇 (CH2) 2-0 //, / C-(CH2) 2-c, 0 (I-23) 〇% 49- 594414 V. Description of the invention (48) CH, — ^ Ch2-c * co 〇

(CH2) 2-%-(0H2) 2- / CH (1-24) " * 3 0

〇 ch3 — (ch2-c_ / C-〇ο ?, (CH2) 2-〇n o (1-25): c- (ch2) 2—c

ch3 C-〇 ^ \ (CH2) 2-0, 々 C — (CH2) 2 — c // o 〇 (1-26)

CH O

3 〇 -50- 594414 V. Description of the invention (49) ch3 ch2-c- ch3-^ ch2-c4- c 1〇 ο // c ~ c Μ, 0

〇 · (1-27)

O

-^ ch2--c4—, c /, ch3 -f ch2—c ten- 〇 // H3c- (1-29) 0-Λ 0

• CH 2 〇 々 c ~ o 〇

CH, // 彳 一 C \ post iH3 〇 h3c (1-31) 3 CH2 ~ CH 4 〇

o o Wide 0 \ /? H3c c —C CH3 ch3 〇_ / S (Bu 32)-c- ch3 gas ch2-c ten · 〇 / C-0 /; // \ tf O (CH2) 2-C \

〇, 〇w / CH (1-33)

0 (1-34). 9 0 -51-594414 V. Description of the invention (50) CH3--CH2 " " C-CH3-f〇H2-c4-co 〇 (ch2) 2-c 〇 Corpse 〇, 〇 // (1-35 )

_ One C, 6 (1-36)

CH3-^ CH2-c_-^ ch2-ch ^-c-o 〇 (ch2) 2-c (o C —〇 々 pu 々 \ // CH3 0 (ch2) 2-c,

(1-37): CH3 — ^ ch2-c-)-

(1-38) 0

G-0 〇

O (CH2) 2-V_-C (eight ^ 9 〇 (1-39) 〇

• ch2-c · CH3 oy c-o

-52- 594414 V. Description of the invention (51 ch3-(ch2-c4- 々c-〇 \ '〇◦' (ch2) 2-〇, // C- (CH2) 2-C · 〇0 H3c (1- 41)

ο ch3 card η2 •-. : 10.c-o. 〇 XCH2) 2-〇n ./γη // C- (ch2) 2-c, ch3 Ό. 〇 H3c- (I-42)

〇 CH3 — (ch2-c-)-c-o. XCH2) 2-〇v / C — (CH2) 2-c 〇 // 0 (I-43)

• ch2 ~ ch j— 〇〇 'n

〇-53- 594414 5. Description of the invention (52) In the present invention, (B) the resin contains a base having an alicyclic hydrocarbon structure represented by at least one of the following general formula (pi) to general formula (pVI) The repeating unit of the protected alkali-soluble group is desired in order to further demonstrate the effect of the present invention. The alkyl group of r12 to r25 in the general formulae (pi) to (pVI) represents a substituted or unsubstituted linear or branched alkyl group having 4 to 4 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl, and the like. In addition, another substituent of the above-mentioned alkyl group is, for example, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a fluorenyl group, a fluorenyl group, a cyano group, a hydroxyl group, a carboxyl group, Alkoxycarbonyl, nitro. The alicyclic hydrocarbon group in ~ R25 or the alicyclic hydrocarbon group formed by Z and a carbon atom may be monocyclic or polycyclic. Specifically, for example, it has a monocyclic, bicyclic, tricyclic, tetracyclic structure having a carbon number of 5 or more. A carbon number of 6 to 30 is preferable, and a carbon number of 7 to 25 is more preferable. These alicyclic hydrocarbon groups may also have a substituent. An example of the structure of the alicyclic part in the base which is an alicyclic hydrocarbon structure in the following. -54- 594414

-55- 594414 V. Description of the invention (54

. (31) (Μ) ㈣ (30) (32) (33) (34) (35) (36) (3T) (3S). (39)

(43)

(40) (^ 1) (42)

(46) (44) ㈣ 0 0 9 9】 【化 18】-

Ο -Ο (47) (48) (49) (50)

-56- 594414 V. Description of the invention (55) In the present invention, the preferred alicyclic part is adamantyl, pro-adamantyl, decane residue, tricyclodecyl, tetracyclodecyl , Orthoalkyl, cedarenol, cyclohexane, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl. Preferred are adamantyl, decane residue, orthospinyl, cedarenol, cyclohexane, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl. The substituents of these alicyclic hydrocarbon groups are, for example, alkyl groups, substituted alkyl groups, halogen atoms, hydroxyl groups, alkoxy groups, carboxyl groups, and alkoxycarbonyl groups. The alkyl group is preferably a lower alkyl group such as methyl, ethyl, propyl, isopropyl, butyl and the like, and more preferably a substituent selected from methyl, ethyl, propyl, and isopropyl. Examples of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group. An alkoxy group (an alkoxy group including an alkoxycarbonyl group) is, for example, one having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of cycloalkyl are cyclopropyl, cyclopentyl, cyclohexyl and the like. The alkenyl group is, for example, an alkenyl group having 2 to 6 carbon atoms, and specific examples thereof include a vinyl group, an allenyl group, a butenyl group, a pentenyl group, a hexenyl group, and the like. Examples of the fluorenyl group include ethenyl, ethylcarbonyl, and propylcarbonyl. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. In the structures represented by the general formulae (Pi) to (PVI), the general formula (pi) is preferred, and the group represented by the general formula (pla) is more preferred. In the general formula (pla), an alkyl group of R28, a halogen atom of R29 to ^ 31, an alkyl group, a cycloalkyl group, a fluorenyl group, an oxo group, an alkoxycarbonyl group, and a fluorenyl group such as the substituents of the above-mentioned alicyclic hydrocarbon group Examples are 0-57-594414. 5. Description of the invention (56) The alkali-soluble groups protected by the structures represented by the general formulae (p I) to (pV I) in the above resins are, for example, various groups known in the technical field. Specifically, for example, a carboxylic acid group, a sulfonic acid group, a phenol group, a thiol group, and the like are preferred, and an acid group or a sulfonic acid group is preferred. Among the above resins, the alkali-soluble group protected by the structure represented by the general formulae (pi) to (pVI) is preferably a group represented by the following general formulae (pVII) to (pXI). -58- 594414 V. Description of the Invention (57)

0 ^ 12! I I —C— 〇1 C—R 13 (PVII!) 14

Bu ο 9 II 丨 ‘C 一 0 ** CH-R 16 o ~ o—c

… (PX) O ^ 22 ^ 23 〇ii. I I ji one C—〇 one C ——CH—: C— R24

R 25 (pix) (pXl), where Ru ~ R25 and Z are each the same as defined above

-59- 594414

V. Description of the invention (58) Protecting the structure The repetition unit constituting the above resin and having an alkali-soluble group represented by general formulae (pi) to (pVI) is represented by the following general formula (PA).

R R

I I ~ ^ 1— 宁 $ — 3R A'-C—0—I? (PA)

II 0 ^ Wherein, R represents a halogen atom or a straight or branched alkyl group substituted with a carbon number of 1 to 4. Several Rs may be the same or different. The halogen atom and the alkyl group are, for example, the same as R in the following general formula (a). A 'is synonymous with the above.

Ra represents any one of the formulae (pi) to (pVI). In the following, specific examples of monomers showing repeating units represented by the general formula (pA) are shown. -60- 594414 V. Description of the Invention (59)

-61-594414

594414 V. Description of the invention (61)

63- 594414

594414 V. Description of the Invention (63)

-65- 594414 V. Description of the Invention (64) 37 38

(B) The resin may contain other repeating units. The resin (B) of the present invention preferably contains a repeating unit represented by the general formula (a) as another copolymerization component. This can improve the developability or the adhesion to the substrate. The alkyl group which may have a substituent in R in the general formula (a) is the same as 1 ^ in the general formulae (I-1) to (1-4). Examples of the halogen atom of R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. At least one of R32 to R34 in the general formula (a) is a hydroxy group, preferably a dihydroxy group or a monohydroxy group, and more preferably a monohydroxy group. -66-594414 V. Description of the invention (65) The resin (B) of the present invention preferably contains a repeating unit represented by the following general formulae (IH-a) to (III-d) as another copolymerization component. This can improve the resolution of the contact hole pattern.

COOH (m-a)

CH2—c *

oh ^ —c-

ch2—c · R5

X ~ 0—C —C-() I -C—C— (^ 1D R-J2

-R (m-b) Z—R13-

-R 14 COO —R-j5 ~ —S〇2 * — 0—R- | 6 (mc) (md) where Ri is synonymous with R above, and R5 to R12 each represent an independent hydrogen atom or may have a substituent Of alkyl. R represents a hydrogen atom or an alkyl group, a cyclic alkyl group, an aryl group, or an aralkyl group which may have a substituent. m is an integer of 1-10. X represents a single bond, or is selected from the group consisting of an alkylene group, a cyclic alkylene group, an arylene group, or an ether group, a thioether group, a carbonyl group, an ester group, an amidinyl group, and a fluorenamine , Urethane group, urea group alone or at least two or more of these groups are combined, and a divalent group that does not decompose by an acid ° -67- 594414 V. Description of the invention (66) z is a single The bond 'ether group, ester group, amido group, alkylene group, or a combination of these divalent groups, and r13 represents a single bond, an alkylene group, an arylene group, or a combination of these divalent groups. R15 represents an alkylene group, an arylene group, or a divalent group of a combination thereof. R14 represents an alkyl group, a cyclic alkyl group, an aryl group, or an aryl group which may have a substituent. R16 represents a hydrogen atom or an alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group, or an aralkyl group which may have a substituent. A is any of the functional groups shown. —C ^ -NH—S02- — S02—NH—C— 〇 〇—NH—C—NH——S02— · — SO〇— NH— C—NH— II II O 〇-- 一 〇 " C NH S〇2-SOp-"NH-C-O II II 0 0-S02-NH-S〇2-R5 ~ R12, R: R14, R16 alkyl groups such as linear, branched alkyl May have substituents. Straight-chain and branched-chain alkyl groups preferably have 1 to 12 carbon atoms and 2 straight-chain or branched-chain alkyl groups, and more preferably 1 to 10 straight-chain or branched-chain alkyl groups. Preferred, more preferred are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl, pentyl, hexyl, heptyl, octyl , Nonyl, decyl. Examples of the cyclic alkyl group of R, R14, and R16 include those having 3 to 30 carbon atoms. Specific examples include cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, orthospinyl, norbornyl, and tricyclic. Decyl, dicyclopentenyl, orthostenyloxy, calenyl, -68- 594414 V. Description of the invention (67) Isofluorenyl, neofluorenyl, tetracyclododecenyl, steroid residues, etc. Examples of the aralkyl group of R, Rm, and R16 include those having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a cumyl group. The alkenyl group of R16 is, for example, 2 to 6 carbons, and specific examples are vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl, cyclopentenyl, cyclohexenyl, cycloheptyl Alkenyl, 3-carbonylcyclohexenyl, 3-carbonylcyclopentenyl, 3-carbonylindenyl, and the like. These cyclic alkenyl groups may also contain oxygen atoms. The bonding group X is selected from, for example, an alkylene group, a cyclic alkylene group, an arylene group, or an ether group, a thioether group, a carbonyl group, an ester group, amidino group, amidino group, and amine A divalent group that is a urethane group or a ureido group alone or in combination of at least two of these groups and that does not decompose by the action of an acid. The 'Z system represents a divalent group of a single bond, an ether group, an ester group, an amidino group, an alkylene group, or a combination thereof. R13 represents a single bond, an alkylene group, or a divalent group combining these. R15 represents an alkylene group, an alkylene group, or a divalent group such as oxo, R13, and R15. For example, the alkylene group has 6 to 10 carbon atoms, and may have a substituent. Specific examples include phenylene, tolyl, and naphthyl. The cyclic alkylene group of X is a divalent group formed by the above cyclic alkyl group. The alkylene group of X, Z, R13, and R15 is, for example, a group represented by the following formula. 1 [C (Ra) (Rbj] r 1 1-69- 594414 V. Description of the invention (68) where 'Ra, Rb represents a hydrogen atom, a radical, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, two It may be the same or different. The fluorenyl group is preferably a lower alkyl group such as methyl, ethyl, propyl, isopropyl, or butyl, and more preferably selected from methyl, ethyl, propyl, iso Propyl. Substituents of substituted alkyl groups such as hydroxy, halogen atom, and alkoxy. Alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy have 1 to 4 carbon atoms. Halogen atoms such as A chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc., rl represents an integer of 1 to 10. Specific examples of the bonding group X are described below, but the content of the present invention is not limited by the present invention.

-70- 594414 V. Description of the Invention (69) _c · II 0

普 c— C-〇eH2〇H2-II πο ο. C-〇ch2ch-o • C-qch2ch2-c- ϋ ^ ^ I! 0.0 c ~ ch2ch2- o- c- ch2ch2— co oo -c-och2ch2 -o—C—D oo / ^ c—oc'h2. 〇: ··,:.

0 -C ~ 0QH2CH2 ~ 0-C; 〇 〇

* C-NH ~ — C 0 ...:, 〇-c

-C-OCH2CH2—MH— C ,. · !! II o · o -c- och2ch2-nh- c-nh— ch2ch2— II II 〇o -C-OCH2CH2-NH — C—NH — CH2CH2— C— 0. 0-0 • C—〇CH2CH2 — NH — C—0— CH2CH2- C— II.. · Π, · 丨 丨 〇ο 〇

-71 594414 V. Description of the invention (70) Other substituents of the above alkyl, cyclic alkyl, alkenyl, aryl, aralkyl, and alkylene groups such as carboxyl, alkoxy, cyano, alkyl, and substitution An alkyl group, a halogen atom, a hydroxyl group, an ethylfluorenylamino group, an alkoxycarbonyl group, and a fluorenyl group. Examples of the alkyl group include lower alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, cyclopropyl, cyclobutyl, and cyclopentyl. Examples of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Ethoxy

Oxygen, etc. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Specific examples of the side chain structure of the general formula (111-b) are specific examples of the terminal structure except X described below, but the present invention is not limited by these.

-72- 594414

V. Description of the invention (71) ~ CH2CH2 — 0 — PH2CH2 — 0H —〇- ch2ch2- ο- ch2ch2— 6— ch3 — 〇η2〇η3; —ο- ch2ch2- ο- ch2〇h2— ο— ch2ch2— oh —o- ch2ch2— o— ch2ch2— o— ch2ch2— o— ch3.. ..... :-0 ~ ΌΗ2〇Η2—O—CH2CH2_ 〇—CH2CH2 ~ 〇—CH2CH3 〇— ch2ch— • o—ch2ch— " 0 — CH3 ch3-.i ..CH3 .- ° 1HCH Factory 0— chch2 — J '-0—ch3 ch3 ch3 —ο- ch2ch— ο- ch2ch— ο— ch2ch— ο- ch3 ch3 ch3 ch3: .. 〇One CH2CH2— ^ 0 One CH2CH2 y ~ 〇_ CH3 —〇- ch2ch2- ^ 0- ch2ch2o- ch3 The following are specific examples of repeating structural units represented by the general formula (I Π-c), but the present invention is not limited by these.

-73- 594414 V. Description of the Invention (72

CH · CH-? ⑵ CH2 = CHI · (3) S02- CH3 〇 // C—NH a S〇2— CH3

ch3 ⑷ CH; 3 CH2 = 〇 o .c—nh-so2-

ch2 = c 0-CH2CH2-O — C-CH2CH2 — C-NΗ ~ · SOf CH30 ο ο (6) CH3 CH2 =? 〇-CH2CH2CH2— S〇2— ΝΗ— S〇2—CH3 (7) 0 ❿- 74-594414 V. Description of the invention (73

ch3CH2 = C ⑻. ^ c- o—CH2CH2〇H2- so2- νη- so2-CH (CH3) 2

0 ch3QH2 = C C 〇 一 CH2CH2CH2—S〇2 — NH-S〇2

(S) o ch3 ch2 = c C- O — CH2CH2 — S〇2 — NH— S〇2 — CH3 (10) ch3 ch2 = c

// o CHp = C c- o— CH2CH2— S02- NH- S02-

(11) ch3 O — CH2CH2 — NH— C_NH — SD2 — C, H3 (12) ch3

CH〇 = C / C— 0 — CH2CH2-NH — C— NH— S02-CH2 (CH2) sCH3 / 11 (.13) ch2 = c ^ C—〇—CH2CH2—NH—C ~ NH—S〇2 〇〆 0

-75 · (14) 594414 V. Description of the invention (74) ch3 CH2 = C I-· ν a 〇 — CH2CH2——〇 一 C a NH — S02—CH3O ’:: ()

ch3 I CH2 = C I-々C— O— CH2CH2CH2 — S〇2—NH— S02 0 * (17)

The following are specific examples of the repeating structural unit represented by the general formula (III-d), but the present invention is not limited thereto. -76- 594414 V. Description of the invention (75 ch3 ch2 = c:? H3 0々CH3 ch2 = cc-o-ch2ch2ch2- s〇2-〇-ch-ch2och3 .⑴: 〇ch3 々〇〇 一 ch2ch2ch2--S02- 〇 一 0h—cii3 ⑵ I ch2 = c ch3; 〇 // C 〇 一 CH2CH2CH2—S〇2 —Q, CH— CH2C1 ⑶ ch3 ch2 = c I ·. X C-0-ch2ch2ch2 ~ S02-0 〇 / ch3 I ch2 = c

〇 ⑷ 〇 々 c-〇 ch2ch2ch2

ch3 I CH〇 = C

〇 〇C 〇 一 · 〇Ι2〇Η2Οί 2—S〇2 — 〇1 CH2 — C—CH3 CH, ⑹ -77- 594414 V. Description of the invention (76 ch3 I ch3 CH ^. C = o 〇 / 一 0-CH2CH2CH2 * tS02-〇-CH2- (Uco〇c (ch3) 3 ⑺ γ CH3. CH2 = C I. -0 — ch2ch2-so2 — o— 〇CH3 ch2 = c

ch2och3 (8) (/ ch3 ch2 = c, c-o—ch2ch2-s〇2 -〇-ch- ch3 ⑼ ch3

-S〇2-0-CH— CH2CI (10) 〇 々

CH2 = C I 〇〇 一 CH2CH2—s〇2—〇 〇 · (11)

〇 (12) ch3 I: ch2 = c I., c ~ 0-ch9ch2ch2-S02-0 n H〇, speaking 〇 々

-78- (13) 594414 V. Description of the invention (77 ch3 ch2 = c ch3 0 ’//, C-0-0¾ (¾ (: ¾ 2 S 〇2-0 2 0¾-; C-Cheng (14)

OH

CH2 = C 0 //, C 〇〇CH2CH2CH2-S〇2 — ο

(15)

CH3 CHn = C 〇 // 〇 1 〇 — S〇2 一 〇

0 b (16)

ch3 I. ch2 = c · I .c-0-ch2ch2ch2 ~ so2 ~ 0 〇 Among them, R5 ~ R12 is preferably hydrogen atom, methyl group is preferred; R is based on hydrogen atom, carbon number is 1-4 alkyl group is preferred , M is preferably from 1 to 6.

-79- 594414 V. Description of the invention (78) In the general formula (111-〇, Ru is preferably a single bond, methyl, ethyl, propyl, butylene, etc., and r14 is based on Cycloalkyl, naphthyl, and naphthylmethyl such as 1 to 10 carbons such as methyl and ethyl, cyclopropyl, cyclohexyl, and camphor residue, naphthyl, and naphthyl methyl are preferred. Z is a single bond, ether bond, Ester bond, 1 to 6 carbon atoms, or a combination of these is better and more preferably a single bond or an ester bond. In the formula (II-I-d), 'R15 is 1 to 4 carbon atoms. The academic group is preferable. Ri6 is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a neopentyl group, an octyl group, and the like having a carbon number of 1 to 8 alkyl groups, a cyclohexyl group, and an adamantane. Base, orthostenyl, norbornyl, isobornyl, cylinyl, morpholinyl, 4-carbonylcyclohexyl, phenyl which may have substituents, tolyl, naphthyl, naphthyl, camphor fei residues Preferably, these other substituents are a halogen atom such as a fluorine atom, a carbon number of 1 to 4 alkoxy groups, etc. In the general formulae (Ilia) to (III-d) of the present invention, The repeating unit represented by the general formula (mb) and the general formula (111 d) is preferable. In addition to the resins mentioned above, when adjusting the dry etching resistance or standard developer suitability, substrate adhesion, photoresist appearance, and resolution, heat resistance, and sensitivity of general requirements for photoresists, it can be used with various Copolymer of monomer repeating units. This repeating unit is equivalent to, for example, the repeating units of the following monomers, but is not limited by them. Thereby, the properties required for the above resin can be fine-tuned, especially (1) for coating Solvent solubility, (2) film-forming properties (glass transition temperature), (3) alkali developability, (4) film periphery (hydrophobicity, alkali-soluble group selection), (5) pair -80- 594414 5. Description of the invention (79) Adhesiveness of the substrate of the unexposed portion, (6) Dry etching resistance. The comonomer has, for example, one selected from the group consisting of acrylates, methacrylates, ammonium acrylates, and formazan Additive polymerizable unsaturated bonds of methacrylic acid amines, allyl compounds, vinyl ethers, acetoyl esters, etc. Specifically, for example, there are acrylates such as alkyl groups (the number of alkyl groups is 1 to 1 0 is preferred) acrylate (e.g. Methyl acrylate, ethyl acrylate, propyl acrylate, pentyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, 3-butyl acrylate, ethyl chloroacrylate, 2-hydroxyethyl acrylate Ester, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, methacrylate Esters, tetrahydroacrylic acid acrylate, etc.); methacrylic acid esters such as alkyl groups (the number of carbon atoms in the alkyl group is preferably 1 to 10); methacrylic acid esters (such as methyl methacrylate, ethyl methacrylate, Propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, ethyl methacrylate, methyl formate Octyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2, 2-dimethyl-3-hydroxypropyl methacrylate, mono Trimethylolpropane methacrylate, monomethyl Pentaerythritol acrylate, methacrylate, tetrahydromethacrylate, etc.); methacrylic acid amines such as methacrylic acid acrylate, N-alkyl methacrylic acid amine (carbon number of alkyl group is preferably 1 to 10 carbon atoms) , Such as methyl, ethyl, propyl, butane

-81- 594414 V. Description of the invention (so) group, 3-butyl group, heptyl group, octyl group, cyclohexyl group, hydroxyethyl group, etc., N, N-dialkylfluorenyl acrylate (alkyl group is carbon Numbers 1 to 10, such as methyl, ethyl, butyl, isobutyl, ethylhexyl, cyclohexyl, etc.), N-hydroxyethyl-N-methacrylamide, N-2-vinylamidine Ethyl-N-ethylammonium acrylate, etc .; ammonium methacrylates such as ammonium methacrylate, N-alkyl ammonium methacrylate (alkyl groups such as 1 to 10 carbon atoms, such as methyl, Ethyl, 3-butyl, ethylhexyl, hydroxyethyl, cyclohexyl, etc.), N, N-dialkylmethacrylamide (the alkyl system is ethyl, propyl, butyl, etc.), N-hydroxyethyl methyl methacrylate, etc .; Allyl compounds are, for example, allyl esters (for example, allyl acetate, allyl hexanoate, allyl heptanoate, allyl laurate, palm Acid allyl ester, allyl stearate, allyl benzoate, allyl acetate, allyl lactate, etc.), allyloxyethanol esters, etc .; vinyl ethers include alkyl vinyl ether (example Hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxy vinyl ether, ethoxy vinyl ether, chlorinated ethyl vinyl ether, 1-methyl-2,2-dimethyl Propyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylamino ethyl vinyl ether, diethylamino ethyl vinyl ether, butyl Aminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofluorenyl vinyl ether, etc.); vinyl esters such as vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate , Vinyl valerate, vinyl hexanoate, -82- 594414 V. Description of the invention (81) Chlorinated vinyl acetate, vinyl dichloride, vinyl methoxyacetate, vinyl butoxylate, ethyl acetate Vinyl vinyl acetate, vinyl lactate, cold-phenyl butyrate, vinyl cyclohexyl carboxylate, etc .; dialkyl itaconates (such as dimethyl itaconate, diethyl itaconate, Dibutyl itaconic acid, etc.); others such as acrylic acid, methacrylic acid, citric acid, itaconic acid, acrylonitrile, methyl Acrylonitrile, etc. Other addition polymerizable partially saturated compounds that can be copolymerized with the various repeating units described above may also be used. The molar ratio of each repeating unit structure in the resin of (B) contains oxygen plasma etching resistance, sensitivity, pattern crack prevention, substrate adhesion, photoresist appearance, The resolution and heat resistance of the necessary elements of general photoresist are appropriately set. The content of the repeating units represented by the general formulae (1-1) to (1-4) in the resin (B) is 30 to 70 mole%, and more preferably 35 to 65 mole% of all the repeating units. The better is 40 ~ 60 mole%. In addition, the content of the repeating unit having a group represented by the general formulae (pi) to (PVI) is 20 to 75 mole%, preferably 25 to 70 mole%, and more preferably 30 to 70 mole% of all the repeating units. 65 mol%. (B) The content of the repeating unit represented by the general formula (a) in the resin is usually 0 to 70 mole%, preferably 10 to 40 mole%, and more preferably 15 to 70 mole% of all monomer repeating units. 30 mol%. In addition, the content of the repeating units represented by the general formula (III-a) to general formula (III-d) in the resin (B) is usually 0.1 to 30 mol% of the total repeating unit, which is -83-594414. Description of the invention (82) The best is 0.5 to 25 mole%, and the more preferable is 20 to 20 mole%. In addition, the content of the resin in the repeating unit based on the monomers of the other copolymer components described above can also be appropriately set according to the desired photoresist performance. However, generally speaking 4) The total repeating unit of the base represented by any one of the formulas and the repeating unit having the base represented by the general formulae (pi) to (pVI) is preferably 99 mol% or less. It is 90 mol% or less, and the most preferable is 80 mol%. The weight-average molecular weight Mw of the resin (B) can be based on polystyrene by the gel permeation chromatography method, preferably from 1,000 to 1,000,000, and more preferably from 1,500 to 500,000. 2,000 to 200,000 is the best, and 2,500 to 100,000 is the best. The larger the weight average molecular weight, the higher the heat resistance and the like, as well as the lower the developability and so on. The balance is adjusted to a better range. The resin (B) used in the present invention can be synthesized by a conventional method, for example, by a radical polymerization method. The following are specific examples of the resin of the present invention (B), but the content of the present invention is not limited thereto. -84- 594414 V. Description of the Invention (83)

ch3 ch3 ch3 ch3-(ch2-c ^ ch2-c ^ -f ch2-c-) ^ ^ ch2-c ^ · c-ch3

IS > c-〇 h3c

c-o ⑷ 〇 h3c

〇 ch3 c one o

〇 -85- 594414 V. Description of the invention (84)

-86- 594414 V. Description of the invention (85) ° Drive CH, ch3 ~ fCH ^ Gvir C-0 C2H5

〇 ch3 ch3 ch3 ch3 *-(ch2-c ^ 弋 ph2-c ^ ^ ch2-c ^ c_〇 c2h5 c-ov ^ .c-ov _

ch3 ch2-c- 0-4 〇Ho o (10) ch3 c-o. ch3

o ❿ 〇 々,. One 0 c2H5 // 〇 c one o (11)

o ch3 — (CH2-ch3 CH2, C · c-10 c2h5ΪΘ o, c—〇 · h3c h3c

(12) 〇 87- 594414 V. Description of the invention (86)

-88- 594414 V. Description of the Invention (87)

-89- 594414 V. Description of the Invention (88)

-90- 594414 V. Description of the Invention (89)

^ CH2 · ^ c one 0, / ^ / c one 10, eight one c CH3 CH3-(ch2-c- 0 positions. Vcr h3c-xian · 6Η (26) 〇

ΌΗ

-91-594414 V. Description of the Invention (90)

92- 594414 V. Description of the invention (91)

-93- 594414 V. Description of the Invention (92)

3

CH-(ch2-c · CH.-^ CH2 · Yan 3: pV.,: • Ga V · r / —〇H O r λ I 〇

CH 3 CH3-fCH2-c, ir CH, / 1 0 ^ iy

-94- 594414 V. Description of the invention (s) CH, ‘,: CH3 -fCH2-C-^-C2H5- ^ CH ^ CvV -iCH2 〇 6 ^-° (40)

CH3-C Ό-ΟΗ 〇 〇

CH3 7CH3-iCH2-c V 4CH ^ CvV, ^ iCH ch3

c-o.? Ha yp ^ ° \ a 0H / \ L 〇 C h3c〆

o

o

CH 3 (41) '〇 ch3 Dec H2-Ct-(CH2-cV-(CH2 o

\ 7 CH c 〇 〇 (42)

ch3 ♦ C-OH 〇

CH 3 CH3 ^ CH2-cV -tCH2-cV-(CH2 · o ch3 iy r / — 〇 〇 H3C h3c (43)

-Flower C-OH O ’〇 -95- 594414 V. Description of the invention (94) ch3 -fCH2-C ^ r TfCH2 ch3 ♦ — ^ ch2- o ch3 o (44) CH,

Wo CH3 -c’f- \ / p — OH 0々 -fCH2- C · \ / m c2h5 • ch2-c · 〇 ch3 -fCH2-C: Gan c-o. H3c h3c (45)

C-OH o ⑩ CH, CH3

~ kCH ^ R \ / m V n CH3 one 〇 \ l] / C H3c CH3 two 4 bids-Su factory ten Shi-cut

〇 々c-0

C-OH 〇 (46) 〇 ch3 CH2-c_ corpse H3 corpse ~ ... card H2 Ί. ~ TCH2 _ C \ V ^ # 二 〇 \ / ^ -0c-0H 0 H3C ^^ 0 h3c 0 / c h3c

❿ (47) CH,

ch3 〇 CH3 p

C —〇 一 (〇Η2〇Η2〇) 2 * ~ CH3 -96- 594414 V. Description of the invention (95)

-97 594414 V. Description of the Invention (96)

CH 2 'ch3, ch3 CH3c ^ r 卬 2-C \ t \ ^ CH3 V-Λ. *, ^-N 々c a o 〇

L 々c-0 < ^. 00 一 知 Η2. ’) 2:% ΓΝ ο ΥΊ, ι Ο 々 ·, ·’.: ,, ： ...

CH3 / CH3 f 7. Dead body 3 card 2-&,-(dog goods ten people ?: work \ 一 〇 CH3 ·: >-〇 person 々 V r \ ο

, 0 (53)

〇 < -c-nh-so2ch3.-98- 594414 V. Description of the invention (97)

-99- 594414 V. Description of the Invention (98) 啐

£ oos — HNIO, / 0 xoo-'VNHoHodos w ^ o) I? A Q. e

Ho bx 0 people 3: ο £ £ or roxo • 0 — 010

, / Ox ox.b NHor ε

Ho o ”Ho 0% β 010- 〇 彳 0 o-” H3r-4 ^ Q ”H3r’. r 11X3 P S) o 0 people \ .5 | 0? ^ 5 | 0 丨. £ 0, £ 01010 £ _ 〇

ε Ho • χοτ £ p

.0,0,0 £ 0 -ο 丨 x'or 010 ε

Ho 6 丨 £ or

° .H 0 £ 0 oio or., Where m, η, p and nl, n2, n3 are all Mohr's ratios of repetitions, with repetitions based on the bases (1-1) to (1-4) The unit is represented by η, and when two or more types are combined, it is represented by nl and η2. With alicyclic hydrocarbons containing (pi) ~ (pVI) -100- 594414 V. The repeating unit of the structure of the invention is represented by m, and the repeating unit shown by the general formula (Ilia) ~ (Illd) Expressed as p. In the case where the units (Ilia) to (Illd) are not repeated, m / n / p is (25 to 70) / (25 to 65) / (3 to 40). When the repeating units shown by the general formulae (III-a) to (Illd) are not included, m / n is (30 to 70) / (70 to 30). The block copolymer may be a random copolymer, may be a regular polymer or an irregular polymer. In the positive-type photoresist composition for far-ultraviolet exposure of the present invention, the amount of the resin (B) in the entire composition is preferably 40-99.99% by weight of the total solid content of the photoresist, and more preferably 50 ~ 99.97 wt%. The positive photoresist composition of the present invention may further contain an acid-decomposable dissolution preventing compound, a dye, a plasticizer, a surfactant, a photosensitizer, and a compound that promotes solubility in a developing solution, as necessary Wait. The positive photoresist composition of the present invention preferably contains a surfactant, and more preferably a fluorine-based / silicon-based surfactant. In other words, a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom, or two or more kinds thereof are more preferable. Such surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 6 1-226745, JP-A No. 62-1 70950, JP-A No. 63-34540, The surfactants described in Japanese Patent Application Laid-Open No. 7-230165, Japanese Patent Application Laid-Open No. 8-6 2 8 3 4 and Japanese Patent Application Laid-Open No. 9-5 98 8 can also be used directly as described below. Commercially available surfactants include, for example, Yebe Dunpu EF301, EF303 (produced by Shin Akita Kasei Co., Ltd.), Floraton fC43〇, FC43 1 (Sum-101-594414 V. Description of the Invention (1 〇〇) Yoshimiya (transliteration) (stock)), Mekafak F171, F173, F176, F189, R08 (Danish Ink (stock)), Safron S-3 82, SC101, Fluorine-based surfactants or silicon-based surfactants such as SCI 02, SCI 03, SCI 04, SCI 05, SCI 06 (made by Asahi Glass). In addition, 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 surfactant is usually 0.001 to 2% by weight, preferably 0.01 to 1% by weight based on the solid content in the composition of the present invention. These surfactants can be used singly or in combination of several kinds. Specific examples of other surfactants include polyethylene oxide lauryl ether, 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, polyepoxy sorbitol fatty acid esters such as polyethylene sorbitol tristearate, and the like. The compounding amount of these other surfactants is usually 2 parts by weight or less, preferably 1 -102- 594414 based on 100 parts by weight of the solid content in the composition of the present invention. 5. Description of the invention (101) Part by weight or less. The (C) acid diffusion inhibitor that can be used in the present invention is preferably added in terms of suppressing changes in sensitivity and resolution over time after exposure to heating and development processing, and more preferably an organic basic compound. The organic basic compound is, for example, a nitrogen-containing basic compound having the following structure. R251; '… (AV _. ··.] ·: Among them, R25〇, R25l, R252 are the same or different hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, and fluorenyl alkyl groups having 1 to 6 carbon atoms A hydroxyalkyl group with a carbon number of 1 to 6 or a substituted or unsubstituted aryl group with a carbon number of 6 to 20, wherein R252 and R252 may be bonded to each other to form a ring. —N—C = N —… ⑻ 1 1 · = C—N = C —… (c) II a. = C—N— ·-• ((D) R254 r255 1 I v R25 a C—N—Q — ^ 256… (E) where R 2 5 3. R254 refers to the same or different carbon bases of 1 to 6. -103- 594414

V. Description of the invention (102)

The nitrogen origin is; Z nitrogen-containing basic compounds, and more preferably two or more different chemical environments are compounds containing alkyl groups containing substituted or unsubstituted amine groups and nitrogen atoms or having alkyl groups. Amine-based compounds. Preferred examples are, for example, substituted or unsubstituted guanidine, = substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, Substituted or unsubstituted imidazole, substituted or unsubstituted pyrazole, substituted or unsubstituted pyrene, 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, etc. . Preferred substituents are amine, amine alkyl, alkyl amine, amine aryl, aryl amine, alkyl, alkoxy, fluorenyl, fluorenyl, aryl, aryloxy, nitrate Group, hydroxy, cyano. More preferred compounds are, for example, guanidine, 丨, 丨 -dimethylguanidine, 丨, 丨, 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, 4-aminoethylpyridine, 3-aminopyrrolidine , Pipe, N- (2-aminoethyl) piperon, 1 ^-(2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinylpiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino -Methyl- -104- 594414 V. Description of the Invention (103) 1-p-Tripyrazole, Pycnogenol, 2- (Aminomethyl) -5 -methylpyridine, pyrimidine, 2,4- Diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-weight Nitrobicyclo [4 · 3.0] -5-nonene, 1,8-diazobicyclo [5.4 · 0] -7- Monoene, 2,4,5-triphenylimidazoline, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinylethylthiourea (CHMETU) Class 3 morpholine derivatives, hindered amines described in Japanese Patent Application Laid-Open No. 11-52575 (described in [0050] in the publication), and the like are not limited thereto. More specific examples are 1,5-diazobicyclo [4 · 3.0] -5-nonene, 1,8-diazobicyclo [5.4.0] -7-undecene (061〇, 1,4 -Diazobicyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrrole, pyrazole, imidazole, dad Cultivated species, pyrimidines, CHMETU, and other third-order morpholines, bis (1,2,2,6,6.pentamethyl-4-piperidinyl) decanoate, and other hindered amines. Among them, 1,5 -Diazobicyclo [4.3.0] -5 -nonene, 1,8 · diazobicyclo [5 · 4 · 0] -7-undecene, 1,4 -diazobicyclo [2.2.2 ] Octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, CHMETU, bis (1,2,2,6,6-pentamethyl-4- Piperidinyl) decanoate is preferred. These nitrogen-containing basic compounds can be used alone or in combination of two or more. The amount of nitrogen-containing basic compounds used is based on the solid content of the entire composition of the photosensitive resin composition. It is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight. If less than 0.001% by weight, the effect of adding the nitrogen-containing basic compound cannot be obtained. If it is more than 10% by weight, the sensitivity will be -105- 594414. 5. Description of the invention (104) The tendency of the image development in the non-exposed part to be deteriorated. The positive photoresist composition of the present invention dissolves the above components. In a solvent, coated on a carrier. The solvent used here is dichloroethane, cyclohexanone, cyclopentanone, 2-heptanone, r-butyrolactone, methyl ethyl ketone, ethylene glycol mono Methyl 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 Ester, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl It is preferable to use ethyleneimine, N-methylpyrrolidone, tetrahydrofuran, etc. These can be used singly or in combination. Among the above-mentioned preferable solvents are 2-heptanone, r-butyrolactone, and ethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, ethyl lactate, methyl methoxypropionate Ethyl ethoxypropionate, N-methylpyrrolidone, and tetrahydrofuran. It is preferable to mix two or more solvents, and the more preferable is a mixed solvent of a hydroxyl-free solvent and a hydroxyl-containing solvent. The positive light of the present invention is The resist composition is coated on a substrate to form a thin film. The film thickness of the coating film is preferably 0.2 to 1 · 2 // m. In the present invention, a commercially available inorganic or organic antireflection film may 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, and an organic film type made of a light absorbing agent and a polymer material can be used. The former must use equipment such as vacuum evaporation equipment for film formation, CVD equipment, and sputtering equipment. The organic anti-reflection film includes, for example, 7-106-594414. 5. Condensate of diphenylamine derivative and formaldehyde-modified melamine resin, alkali-soluble resin, and light absorption as described in invention description (105) 696 1 1. Agents, or reactants of maleic anhydride copolymers and diamine-type light absorbing agents described in U.S. Patent No. 5,294,680, Japanese Unexamined Patent Publication No. 6-1 1 863 1 contains resin binders and methylolmelamine-based heat. For a crosslinking agent, an acrylic resin-type antireflection film having a carboxylic acid group, an epoxy group, and a light-absorbing group in the same molecule described in Japanese Patent Application Laid-Open No. 6-1 1 86 56 is described in Japanese Patent Application Laid-Open No. 8-87115. Of hydroxymethyl melamine and benzophenone-based light absorbing agents, and those containing a low-molecular-weight light absorbing agent in the polyethylene glycol resin described in JP-A-8-1 79509. In addition, the organic anti-reflection film can also use DUV30 series or DUV-40 series manufactured by Newark Sainz Co., Ltd., and AC-2 and AC-3 manufactured by Western Lightning Co., Ltd. The above photoresist liquid is applied to a substrate (such as a silicon / silicon dioxide coating) used in manufacturing precision integrated circuit elements (on a substrate provided with the above-mentioned antireflection film as needed) 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 photoresist pattern is produced by development. Here, the exposure light source is preferably light having a wavelength of 150 nm to 250 nm. Specifically, there are, for example, KrF excimer laser (248 nm), Ai: F excimer laser (193 nm), F2 excimer laser (157 nm), X-ray, electron beam, and the like. 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 triethylamine, methyldiethylamine, etc. -107- 594414 V. Description of the invention (106) Alcohol amines such as amine 'dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, Aqueous solutions of quaternary ammonium such as tetraethylammonium hydroxide and cyclic amines such as pyrrole and pyridine. In addition, an appropriate amount of an alcohol or a surfactant may be added to the alkaline aqueous solution. [Examples] The present invention will be described in more detail by examples and the like in the following, but the present invention is not limited by these. [Synthesis of the photoacid generator of the component (A)] In the following, two examples of the photoacid generator of the component (A) are synthesized. The other photoacid generators used below are the same method, or Those who synthesize the above-mentioned general methods may use commercially available ones. The following photoacid generators are those manufactured by Green Chemical Co., Ltd. Triphenylene perfluoro-n-butanesulfonate: (A1- 1), (A2-4) triphenylsulfonium trifluoromethanesulfonate: (A2-1) bis (3-butylbenzene Iodine hydrazone) Perfluoro-n-butane sulfonate: (A1-49) [Synthesis of triphenylene perfluoro-n-octane sulfonate (A1-3)] 50 g of diphenylene Dissolved in 800 ml of benzene, 200 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. The aqueous solution was washed with 500 ml of ethyl acetate, and after filtration, 400 ml of 200 g of ammonium iodide was dissolved. The precipitated powder was filtered, washed with water, and then washed with vinegar -10 8- 594414. V. Description of the invention (107) The ethyl acetate was washed and dried to obtain 70 g of triphenyl iodide. 17.6 g of triphenyl erythroiodide was dissolved in 1,000 ml of methanol, and 12.5 g of silver oxide was added to the solution, followed by stirring at room temperature for 4 hours. The solution was filtered, and 25 g of a solution of perfluoro-n-octanesulfonic acid in methanol was added thereto. The reaction solution was concentrated, and the precipitated oil was dissolved in ethyl acetate, washed with water, dried, and concentrated to obtain 20.5 g of the desired product. [(Synthesis of tris (3-butylphenyl) fluorene perfluoro-n-butanesulfonate (A1-5) and (A2-8)) Di (3-butylphenyl) sulfide (80 mmol), a mixture of di (3-butylphenyl) iodine perfluoro-n-butane sulfonate (20 mmol), copper benzoate (4 mmol), under a stream of nitrogen Stir at 130 ° C for 4 hours. The reaction liquid was cooled, and 100 ml of methanol was added thereto to remove precipitates. When filtration was concentrated, and 200 ml of ether was added thereto, the powder was precipitated, filtered, washed with ether, dried, and the target substance was obtained. [Synthesis of the resin (1) of the present invention] In a molar ratio of 50/50, 2-methyl-2-adamantyl methacrylate and 6-endo-hydroxybicyclo [2.2.1] heptane- 5-Exo-methacrylic acid ester of 2-endo-carboxylic acid-r-lactone, dissolved in N, N-dimethylacetamidamine / tetrahydrofuran = 5/5, adjust the solid content concentration of 100ml to 20% Its solution. 6-endo-hydroxydihydro [2.2.1] heptane-2-endo-carboxylic acid-r-lactone 5-exo-methacrylate is used to make 6-endo-hydroxybicyclo [2 · 2 · 1 ] Heptane-2 -endo-carboxylic acid ethoxylate-lactone, the ethoxylate base is hydrolyzed to hydroxyl groups, and then synthesized by methacrylic acid chloride esterification. By the method described in i. Chem. -109- 594414 V. Description of the Invention (108) Soc ·, 227 (1 959), Tetrahedron, 21, 1 501 (1 965). To this solution was added 3 mole% of v-6 manufactured by Wako Pure Chemical Industries, and 10 ml of N, N-dimethylacetamidine heated to 60 ° C was added dropwise under a nitrogen atmosphere within 3 hours. Lamine. After the dropping was completed, the reaction solution was heated for 3 hours, and then added with 1 mole 65, followed by stirring for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature, crystallized in 3 L of distilled water, and the precipitated white powder was recovered. The polymer composition obtained from C13NMR was 51/49. The weight average molecular weight in terms of standard polystyrene obtained by GPC measurement was 7,200. The resin examples (2) to (59) shown above were synthesized in the same manner as the above synthesis example. Table 1 shows the molar ratio of the repeating units (the order of repeating units shown in each resin example is from left to right) and the weight average molecular weight. -110- 594414 V. Description of the invention (109) Table 1 Resin composition ratio (molar ratio) Weight average molecular weight (1) 5 1/4 9: 7 2 0 .D (2) 40/60 113 0 0 ( 3) 4 5/5 0 1 6 4 0 0 (4) 5 0/15/1 5/2 0 • 6 4 0 0 (5) 5 2/4 8 ^ „8 4 0.0 (6) 5 0/5 0 1 0 2.0.0 (7) 4 0/2 0/2 0/2 0 8 7 0 0 (8) 5 2/4 8 8 5 0 0 (9) 3 0/7 0 2 10 0 0 (10 ) 4 0/2 0/2 0/2 0 .12000. (11) 5 0/5 0-4.6 0 0 (12) 4 5/5 5 2 3 0 0 0 (.13) 6 0/15/1 5/10 1 2 2 0 0 (14) 3 5/6 5: 14500 (15). 5 0/5 0 1 0 5 0 0 (16) 4 0/2 0/2 0/2 0 5 7.0 0 ( 17) 4 9/5 1 7. 6 0 0 (18) 4 2/5 8 丨 1.4 3 0 0 (19) 3 5/1 5/2 5/2 5 1 2 0 0 0 (2 0) 4 9 / 3 1/2 0 1 2 5 0 0 (2 1) 5 0/4 0/1 0 1 3 2 0 0 (2 2) 3 0/5 0/2 0 1 .0.3 0 0 (2 3) 35 / 55/10 1 4.6 0.Ό .. (2 4) 4 0/4 0/2 0 1 3 7 0 0 (2 5) 5 0/4 0/1 0 9 8 0 0 (2 6) 2 5 / 7 0/5 7 5 0 0 (2 7) 3 5/6 5/1 0 5 6 0 0 (2 8) 51/28/21 9 7 0 0 (2 9) 3 0/5 0/2 0 6 7 0 0 (3 0) 50/30/20 11 300.

-111- 594414 V. Description of the invention (11〇) Table 1 (continued) Resin composition ratio (molar ratio) Weight average molecular weight (3 1) 4 0/6 0 9 3 0 0 (3 2) 5 0/5 0 6 5 0 0 '(3 3) 5 5/45 1 5 0 0 0 (3 4) 3 5/6 5 1 5 4 0 0 (3 5) 5 5/4 5 1 6 2 0 0 (3 6) 4 5/5 5 12 2 0 0 (3 7) 3 0/7 0 -V 9〇〇〇 (3 8) 4 7/4 5/8; * 8 9 0 0 (3 9) 45/45/10 ; 1 3 3 0 0 (4 0) 5 0/4 5/5 1 0 2 0 0 .. (4 1) 4 0/5 0/1 0 V 1 7 4 0 0 (4 2) 5 0/4 5/5 • " 7 1 0 0 (4 3). 45/40/15 .7600. (4 4) 4 0/4 0/2 0 2 10 0 0 (4 5) 46/44/10.: 9300. (4 6) 4 0 / 5,0 / 1 0 1 3 2 0 0. (4 7) 3 5/5 0/1 5 2 2 0 0 (4 8) 4 5/5 0/5 1 3 2 0 0 (4 9) 4 0/5 0/1 0, 6 9 0 0 5 (5 0) 5 0/4 0/1 0 .5 5 0 0 (5 1) 4 5/4 5/1 0 9 9 Ό 0 (5 2) 4 0/5 0/1 0 ^ 1 2 3 0 0 (5 3) 4 5/4 5/1 0 v 1 4 3 6 0 (5 4) 5 0/4 3 / 7 7 10 0 (5 5) 4 8/4 8/4 1 4 2 0 0 (5 6) 4 5/4 5/1 0 1 6 3 0 0 (5 7) 5 5/4 0/1 0 .11000 (58) 4 0/5 0/1 0 1 4 2 0 0 (5 9) 4 7/5 0/3 1 5 2 0 0 Examples 1 to 59 and Comparative Examples 1 to 5. Synthesis of the above Examples of synthetic resins and each described in Table 2 After 12 minutes a solid content weight ratio of the% dissolved in the solvent described in Table 2, to 0. 1 // m micro-filtration filter, adjusting Example 1~59, Comparative Examples 1 ~ 5 of the positive photoresist. The components of the composition of the present invention are shown in Table 2.

-112- 594414 V. Description of the Invention (111) Table 2

Example resin acid generator acid diffusion inhibitor interface cleaner active agent. _ (Weight ratio) ... A1 (added lg) A2 (added amount g) 1 1 A—Bu 1 (0, 1). A2- K0.1) ::;; ^ Bl (0'05) W_1 丨 PGMEA 2 2 A 3 A2-4 (0; l) Β2 (0 · 02Μ Look at 'Heart 丨' 3 3 A1-5 (0.2): β · Α2-5. (0 · 2) ::: Β3 (0:04) :: _ :; W-2 PGMEA 4 4 Al-7 (0.2) A2-4 (0.l): B4 (Gr005) -: Wl ·. PGMEA- i 5 5 Α1 · 3 (0, i) A2-3 (0.3) Β5 (0 ·· 01) ·: 丨 W-4 .. 'PGMEAJ 6 6 Al-21 (0.1) ¾ Α2-Φ.2) y; i ^ *. _05) .I PGMEA / PGME!., (8/2) · 7 7 Al-49 (0.3). ··) .; ^ A2-43 (0, l) 〇 (Β2 (0 · 02) CH ··· 8 8 M-43 (0.1) ·, ', A2-K0.1): · Β3 (0.04)': W-3 · '· BL · 9 9 Al-1 (0V3) '... A2-K0.1) r: (• B4 (0.005): PGMEA / BL:, (9/1) 10. 10 Al-5 (0,2) A2-5 (0A ) B5 (0.01) PGMEA ·: 11 11 AMi (0.2) H: v Α2-ΙΪ (0.2) / i Bi (ii.oi); W-2-: PGMEA / PGHE 丨. (8/2) 12 12 Al-5 (0: i). 'A2-i (0,4) B2 (0.02) -y -WL PGMEA / PGHE 13 13 Al-2 (0.3) < · Α2-4 (0 · 2) BH0 .05) tf-4PGMEA 14 Η Al-8 (0.2) A2-l (0.2) B2 (0.02) W-3 PGMEA 15 15 Al-54 (0v2): i;-A2-47 (0.05) · _ · 〇4) wl .. PGMEA. 16 16 Al-4 (0; 1) ... A2 -4 (0.2) B4 (0.005) W-4; PGMEA 17 17 Al-3 (0.1): A2-4 (0.1). _ · 01). Tf-2: PGMEA 18 18 A 5 < 0.2) Α2 < (0 · 2)… 二. Bl (0.03) •! Wr PGMEA 19 19 Al-7 (0.2) A2-4 (0.1) 81 (0,05.) Wl PGMEA 20 20 Al-85 (0.1) " A2-72 (D.5) B2 (0,02) .. • W-4 ... PGMEA 21 21 A 85 (0.075)-A2-60. (0.3): • B3 (0 · 04) two PGMEA -11 ', 22 Α1-7Ϊ · (0.2): A2-64 (D.2) B4 (0.005) Wl ·. PGHEA 23 23 Al-65 (0.3) .. A2-K0.1) .. B5 ( 0,01): ΨΙ: PiMEA · 24 24 Al-69 (0.3)-^. A2-72 (0.3) · :, Bl (d; 05) 'V ..Wl. PQBEA / PGHE (8/2) '25 25 Al-81 (0.15) A2-K0.05): Β2 (0 · 02) W-2. CH. 26 26 A 82 (0.1) A2-64 (0.3) Β3 (0 · 04) W -3. BL 27 27 Abu 83 (0,1) · 'Α2-60 (0 · 2)' Β4 (0 · 005) Wl PGMEA / BL (9/1) 28 28 AM (0.1) · '. A2 -K0.1) B5 (0.01) W-4 PGHEA 29 · 29 Al-3 (0.1) Α2-4 (0 · 1) Bl (D.Ol) 'W-2 PGMEA / PGME (8/2) 30 30 Al-5 (0.2) · _ A2-5 (0.2) Β2 (0 · 02)… • ΊΗ, PGMEA / PGHE ( 8/2) 31 31 A7 (0.2) AM (〇 · 1) BK0.05) W-4 'PGMEA 32 32 Al-3 (0.1) A2-3 (0 · 3) B2 (D.02) W -3 PGMEA 33. 33 Al-21 (0.1) Α2-15 (0 · 2) B3 (D.04) W-ί PGMEA 34 34 Al-49 (0.3) A2-43 (0.L) B4 (O. OOS) W-4 PGMEA

-113- 594414 V. Description of the Invention (彳 12) Table 2 (Continued)

Example Resin Generator: ···; Acid Diffusion " Inhibitor Surfactant Activator: ΊA1 (add igK: A2 (addition amount 35 35 AM3 (0.1), A2-K0.1) 0 Β5 (0 · 01) n PGHEA :: 36 36; A1-1 (0.3) vi Α2-1 (0 · 1) :: ㈤ BU0.03) PGMEA r 37 37 heart 5 (0.2) ',! Α2 -5 (0,4) ι · * ΒΚ0.05): Μ · ι PGMEA · 38 38 A1-11 (0.2): Α2-1Κ0.2)? 2 (0.02) .. W-4. [PGMEA 39 39 A1-5 ·· (0.!) A2-l (0,4) Β3 (0.04) Μ PGMEA 40 40 A1-2 (0.3) Α2-4 (0 · 2)!, Μ (0.005) ΊΗ 'PGMEA., 41 41 A1-8 (0.2) Α2-Κ0.2): Γ Β5 (0,01) ίΗ 卜 "PGMEA ... 42 42 A1-54 (0: 2)' · 'Α2- 47 (0 · 05) 乂 η BK0.05) V-1 y PGMEA / PGME (8/2) 43 43 Α1 · * 4 (0 · 1): Α2-4 (0.2). Β2 (0 · 02) > 2-CH 44 44 Al-3 (0: 1)-Α2-4 (0.ΐ) Β3 (0 · 04) W-3 _ BL 45 45 A1-5 (0.2) Α2-5 (0 · 2) Β4 (0.005) W-1 PGMEA / BL · (9/1) 46 46 Αί-7 (0.2) Α2-4 (0.1) Β5 (0.01) tf-4 · PGMEA 47 47 AL-85: (0.1): Α2 -? 2 (0 · 5), ΒΙ (Ο, ΟΙ) • • tf-2 PGMEA / PGME ,: (8/2) 48 48 A1-85 (0.075) Α2-60 (0.3): '· ί. R Β2 (0 · Ό2) _ _ " tf-1-: PGMEA / PGHE. 49 49 A1-71 (0,2)-.. Α2-64 (0.2) Β1 (0 · 05) W-4 v PGMEA 50 50 A1- 65 (0.3): Α2-Κ0-1) Β2 (0.02) W-3 PGMEA 51 51 A1-69 (0.3) · /12-72(0.3) Β3 (0.04) Wl · PGMEA 52 52 A1-81 (0.15 Α2-Κ0.05) Β4 (0,005) V-4 PGMEA 53 53 Αί-82 (0.1), =-Α2-64 (0,3) Β5 (0.01) W-2 · PGMEA 54 54. ΛΙ-83 (0.1). Α2-60 (0 · 2). Β1 (0.03) Wi PGMEA 55 55 AH (0.1) Α2-Κ0.1). ΒΚ0.05) · ΊΗ PGMEA 56 56 Al-3 (0.1) Α2- 4 (0.1) Β2 (0.Ό2) 14 PGMEA 57-57 Al-5 (0.2) Α2-5 (〇 · 2) Β3 (0.04) W ~ 2 ~ PGHEA 58 58 Al-7 (0.2) Α2-4 (0,1) 84 (0.005) 1-1 PGHEA 59 59 Al-3 (0.1) A2-3 (0.3) B5 (0,01) tf-4 PGMEA Comparative Example 1 1 λΗ (0.2) Bl (fl.OS ) M.PGHEA 2 1 A2-K0-2) Β1 (0.05) Wi PGHEA 3 Z Ai-1 (〇a) A2-U0.1) BK0.05) WL PGHEA 4 Z AH (D.2) ΒΚ0. 05) tf-L PGMEA 5 Z Α2-Κ0.2) ΒΚ0.05) tf-i PGMEA Each symbol in Table 2 is as follows.

-114- 594414 V. Description of the invention (彳 13) [Resin] Resin Z: 2-methyl-2 -adamantyl methacrylate- mevalonyl methacrylate (50/50), weight Average molecular weight 6900 < [Acid diffusion inhibitor] B-1 DBN; 1,5-diazabicyclo [4.3.0] non-5-ene B-2 TPI; 2,4,5-triphenylimidazole B -3 DCMA; Dicyclohexylmethylamine B-4 2,6-diisopropylaniline B-5 TPSA; Triphenyladenoacetate [Surfactant] W-1:: Mekafak F1 7 6 (made by Dainippon Ink Co., Ltd.) (fluorine-based) W-2: Mekafak (translated) R08 (made by Dainippon Ink Co., Ltd.) (fluorine-based and polysiloxane) W-3 :: Polysiloxane polymer-KP-341 (made by Shin-Etsu Chemical Industry Co., Ltd.) W-4: Dunlong Yilulu (transliteration) S- 366 (made by Dunlong Yilu Chemical Co., Ltd.) [ Solvent] PGMEA ·· propylene glycol monomethyl ether acetate PGME :: propylene glycol monomethyl ether CH · cyclohexanone BL · r-butyrolactone < day image evaluation method > (1) Resolution 'exposure range, Evaluation of Density Correlation and Line Edge Roughness-115- 5944 14 V. Description of the invention (114) A spin coater was used to uniformly coat the anti-reflection film DUV-42, manufactured by Minervaisenes Co., at 600 angstroms with a silicon substrate treated with hexamethyldisilazane. After drying on a hot plate at 100 ° C for 90 seconds, heat drying was performed at 190 ° C for 240 seconds. Then, each photosensitive resin composition was coated with a spin coater and dried at 120 ° C for 90 seconds to form a 0.3 / m photoresist film. This photoresist film was exposed through a photomask and an ArF excimer stepper (NA = 0.6 manufactured by ISI). After the exposure, the photoresist film was directly heated at 120 ° C on a hot plate for 90 seconds. In addition, the solution was developed with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C for 60 seconds, washed with pure water for 30 seconds, and dried to obtain a photoresist line pattern. [Resolution power]: The resolution power is the critical resolution for the amount of exposure to reproduce the mask pattern of 0.1 3 // m. [Exposure range]: Make the exposure amount of the mask pattern reproduction of 0 · 1 3 // m and the gap (1/1) as the optimum exposure amount, and divide the exposure amount of the line width reproduction of 0.13 // m ± 10% by The ratio of the optimal exposure amount is expressed as 100% (%). The larger the number, the smaller the change in line width for the change in exposure. [Sparse and dense correlation] In the line and gap pattern of line width 0. 1 3 // m (dense pattern: line and gap 1/1) and isolated line (sparse pattern: line and gap 1/5), find each A range where 0 · 1 3 # m ± 10% of the focal depth overlap is allowed. The larger the range, the better the sparse correlation. [Edge Roughness]. Regarding the range of the longitudinal edge of the isolated line pattern in the range of 5 // m from the edge -116- 594414 V. Description of the invention (115) The distance of the reference line of the edge is measured using a length measurement SEM ((share) Hitachi S-8840 manufactured by Seisakusho Co., Ltd. was measured at 50 places, and the standard deviation was calculated to calculate 3σ. A smaller 値 indicates better performance. The results are shown in Table 3. -117- 594414 V. Description of the invention (116) Table 3 実 Example resolution ium). Dew. (%). ¾ Ning 窀 dependency. · ^ Ijum) (nm). 1: 0: 115 1L2 '' 0.9 3 · · 2 • 0.11 12.5… 1 · 1 -4 '\' 3 叽 11 13,7: ii, 3 4 0.115 11 · 1 0.9 5, 5 0.115 11 · 3 0.9 3 6 0.11 13 · 6 .1 · 0. , 6 7 0,11 13.9, 1.1 5 8 0.115 12.2 L2 4 9 0.11 11 · 5 0.9, · 6 10 0.115 12,8 1.0 4 11 0.115 13 ·· 3 1 · 1 5 12 0.11 13.8 L0 5 ·· 13 0.115 11 · 1 1 · 0. 3 14 0: 115 12.0 0.9 4 15 0.11 13,7 1,2 5 16 0.115 12.2 0.9 5 17 0.11 11.9 ， 0.9 6 ， 18 .0,115 .12.1 1,0 4. 19 0- 115 13.4 '1 · 1 4 20 0.11 11.2 1,1 3 21 0.11 11.8. 0,9 3 22 0.11 12.7 1Λ 4 23 0:11 13.3 L0 4 24 0: 115 13.6 L2 5 25- 0.11 11.8 0 · 9 6 26 0,115 12,9 1.0 4 27 0.115 13.2 1.1 5 28 0,115 12.1 1.2-4 29 0:11 .11.5 • 0.9 3 30 0.11 12.7 1.0 4 31 0.115 13.0 ll · 5 32 0 · 11 11.1 1 · 9 5 33 0.11 11,1 0-9 3 34 0.115 12.2 1.0 · 4 35 0.11 13.7 1.1 4 -118- 594414 V. Description of the invention (117) Table 3 (continued) 実 Example resolution \ (jum) ： Y. Lu Guang ·: · (%) Close dependence. (/ Im) _ ·; 7 < yivr77n ^ ... (ηm 一 36. 0.115 11.1. 1 · 0 ..... \. 3 · :: 37 0-115 12.6 1 · 0 4., 38, 0 · 11 13.7 1.2 —. ·: · 5 .. 39 i.0,11 13.8 LI. 5: 40 .0.11 · 11.3 .0.9 3 41 0.115 12.2 1 · 0 · ... 4 42 0.11 13.6 '1 · 0 6 43 0 · 115 12.4 1,1 .. 3. 44 0.11 11.7 1 «0 ..... 3 45 0.11. 12 · 6 1.0 4 46 0.11 13.8- 1 · 1 5 47 0.115 • 11.3 0.9 5 48 0.11 11 · 9 0,9 6. 49 0.115 12 · 2 1.0 4 50 0.11 13.4 1 · 1 3 51 0.115 12.3 0.9 5 52 0.11 .11 · 1 · 0.9 * 5 53 0,11 12.5 1.0 4 54. 0.11 13,6 1.1 3 55 0.11 14.0 1.1 5 56 0.11 11.4 0.9 4 57 .0.115 12.8, • 1 · 0 3. 58 0 · 11 13.9 1.1 5 59 0.115 14 · 0 1 L2 6 Comparative Example 1 0.12 4.6. 0Α 7 2 0.13 2.0 0 · 3 7 3 0.12 7.8 0.8 11 · 4 0.12 5 · 3 0 · 4 10 5 0.13 2.0 0.2 12 -119 · 594414 5. Description of the invention (118) As a result, it was found that the positive photoresist compositions of the present invention all had satisfactory levels. In other words, it is suitable to start with ArF excimer exposure and use lithography with far ultraviolet rays. EFFECT OF THE INVENTION The present invention can provide a positive photoresist composition suitable for far ultraviolet light, particularly A rF excimer laser light, which has excellent resolution, exposure range, denseness and correlation, and line edge roughness. -120-

Claims (1)

594414 VI. Application for Patent Scope No. 9 1 1 1 3909 "Positive Photoresist Composition" Patent (Amended on February 20, 1993) Λ Application Patent Scope: 1. A positive photoresist composition, which Containing: (A) a sulfonic acid salt selected from the group consisting of anions represented by cations consisting of iodine or fluorene and anions having RFS03 (wherein RF is a fluorine-substituted alkyl group having 1 to 20 carbon atoms), and at least two The carbon number difference of the RF of each anion part is 2 ~ 15. The photoacid generator which generates acid by irradiation with active light or radiation, which accounts for 0.001 ~ 40% by weight in the total solid content, (B) A resin containing at least one repeating unit represented by the following general formulae (1-1) to (1-4) and decomposed by an acid to increase solubility in alkali, which accounts for 40 to 99.99 of the total solid weight%, (Among them, Ri ~ R5 represents the same or different, hydrogen atom, and may have 594414. 6. The alkyl group, cycloalkyl or alkenyl group of the substituted patent application group. Two of L ~ R5 can be bonded to form a ring.) . 2. If the positive photoresist composition according to item 丨 of the patent application range, wherein the (A) component is relatively large in carbon number, the photoacid generator is selected from the anion portion, and the RF number is 4 to 20 linear carbons. A photoacid generator having a fluorine-substituted alkyl group, and a photoacid generator having a relatively small carbon number in RF is selected from 6 to 6 carbon atoms in the anion portion of the linear substituted alkyl photoacid generator. 3. If the positive photoresist composition of item 1 of the patent application scope, wherein the cationic portion of at least one photoacid generator is represented by the following formula (I), (11), or (I I I), -2-594414 6. Scope of patent application ^ 35 dll) (where Ri ~ R37 represent the same or different hydrogen atom, straight chain, branched or cyclic alkyl group, straight chain, branched or cyclic alkoxy group, hydroxyl group, halogen atom , Or-S-R38, r38 represents a linear, branched, or cyclic alkyl or aryl group, and two or more of Ri ~ R15, r16 ~ r27, or r28 ~ r37 can be combined to form one species Or two or more selected from the group consisting of a single bond, a ring of carbon, oxygen, sulfur, and nitrogen). 4. The positive photoresist composition according to item 1 of the patent application scope, wherein (B) the resin further contains an alicyclic hydrocarbon represented by at least one of the following general formula (PI) to general formula (PVI) Repeating unit of alkali-soluble group protected by structural base, (Pi) C .R '21 4 R11 C1R1 (PI (pin) 〇. I —CH — -3-——- j 594414 R r I23, i? C * CH— C——R 24 (pV) 〇1 0 = c · R. wf. \} / Fou (wherein Ru is methyl, ethyl, n-propyl, isopropyl Group, n-butyl group, isobutyl group, or 2- butyl group, Z is a carbon atom and an atomic group necessary to form an alicyclic hydrocarbon group, and R12 to Ru each represents an independent carbon number of 1 to 4 straight or branched chain alkane Or alicyclic hydrocarbon group, at least one of Ri2 to Ri4, and any one of R15 and R16 is an alicyclic hydrocarbon group, and R17 to R21 each represent a hydrogen atom, and 1 to 4 carbon or straight chain alkyl groups An alicyclic hydrocarbon group, at least one of R17 to R2i is an alicyclic hydrocarbon group, and any one of R19 and R21 is a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, and R22 to R25 each represent Independent carbon numbers of 1 to 4 linear or branched alkyl or alicyclic hydrocarbon groups, and at least one of R22 to R25 is an alicyclic hydrocarbon group). 5. The positive-type photoresist composition according to any one of claims 1 to 4 in the patent application scope, which contains an alicyclic hydrocarbon structure represented by the general formula (pi) to the general formula (pVI) — 4 — 594414 6. The scope of patent application is based on the following general formula (PIa) (pla) (wherein r28 represents an alkyl group which may have a substituent, and r29 to r31 represent a hydroxyl group, a halogen atom, a carboxyl group, or an alkyl group, a cycloalkyl group, an alkenyl group, or an alkyl group which may have a substituent Oxy, alkoxycarbonyl or fluorenyl, p, q, and r each independently represent an integer of 0 or 1 to 3). 6. The positive photoresist composition according to any one of claims 1 to 4 in the scope of the patent application, wherein (B) the resin contains a repeating unit represented by the following general formula (a), ~ fcH2-c)-C * —- 0 I 0 (a) R33 (where R represents a hydrogen atom, a halogen atom 'or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, R32 to R34 represent the same or different hydrogen atom or hydroxyl group, and at least one of R32 to R34 Is hydroxyl). -5 a