TWI304060B - Acid generator and radiation-sensitive resin composition - Google Patents

Description

1304060 DESCRIPTION OF THE INVENTION (1) Background of the Invention The present invention relates to an acid generator, a sulfonic acid, a sulfonic acid derivative, and a radiation-sensitive resin composition. More particularly, the present invention relates to a photoacid generator suitable for use in a radiation-sensitive resin composition, which is used for utilizing various types of radiation, for example, deep ultraviolet light such as KrF a molecularly amplified laser, an ArF excimer laser, an F2 excimer laser, or an EUV (extreme ultraviolet light), a x-ray such as a synchrotron radiation, or a charged particle beam such as an electron beam micro-fabricated chemically amplified photoresist; a sulfonic acid produced by the acid generator; a sulfonic acid derivative useful as a raw material or intermediate for synthesizing the acid generator; and a positive-tone or negative-type radiation-sensitive one containing the acid generator Resin Composition 0 Description of the Art In the fabrication of integrated circuit devices, it is possible to microfabricate 0. 20 microns or less to achieve a higher buildup. The conventional lithography method utilizes the near-ultraviolet linewidth that is known to be difficult to use in the art. In the field of microfabrication, there is a need for linewidth lithographic ultraviolet light, such as i-ray radiation. The wire microfabrication is less than a quarter of a micron or less. Regarding the shorter shots in microfabrication 〇.2〇 micro; the line spectrum of the excimer laser is;; the light shot is the mercury beam and so on. Among them, κ r F quasi-division of external light ^ ray, electricity: per shot (wavelength: 248 nm (nm)),

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ArF excimer laser (wavelength · · 193 nm), F2 excimer laser (wavelength · · 157 nm), EUV (wavelength: 13 Nai), and electron beam are subject to attention. With regard to radiation-sensitive resin compositions which can be applied to shorter-wavelength radiation, many photo-acid generators which utilize an acid-cleavable functional group and when irradiated: hereinafter referred to as "exposure" have been proposed. The composition of the chemical amplification effect between. Hereinafter, this '~ composition is referred to as a chemically amplified light-sensitive sensitive composition. Regarding the chemically amplified radiation-sensitive composition, Japanese Patent Publication No. 276 60/190 discloses a polymer comprising a third butyl carbonate group containing a carboxylic acid or a second butyl carbonate group of a phenol, and photoacid generation. The composition of the agent. This composition can form an acidic group (such as a slow group or a phenolic hydroxyl group) by utilizing the effect of the polymer releasing the third butylate group or the dibutyl carbonate group by the action of an acid generated upon exposure. The exposed areas on the photoresist coating are readily soluble in the developer. The characteristics required for chemically amplifying the photoacid generator of the radiation-sensitive composition include excellent transparency to radiation, high quantum yield, and generation of a strong acidity, a high boiling point, and a coating in a photoresist. Suitably, the ability to hereinafter be referred to as the acid of the diffusion length). ^ In order to ensure high acidity, high boiling point, and appropriate diffusion length, the structure of the anionic group in the ionic photoreceptor and the nonionic photoacid generator containing the sulfonate structure or the sulfonate structure The structure of the sulfonyl group is quite important. For example, when the photoacid generator has a trifluorosulfonyl sulfhydryl structure, although it produces a sufficiently strong acid which ensures the proper resolution performance of the photoresist, it has a low boiling point and a long diffusion length due to the generation of acid. Therefore, the reticle phase 1304060 five, the invention description (3) ------- the disadvantage of the high (mask dependency). When the photoacid generator contains a sulfonium-based structure of a large organic group such as a 10-camphorsulfonyl structure, although the photomask correlation is low due to the high boiling point and short diffusion length of the acid, it is used as light. The resolution performance of the resist is insufficient due to poor acidity. On the other hand, a photoacid generator having a perfluoroalkanesulfonyl structure (such as perfluorooctanesulfonic acid (PFOS)) has been subjected to recent years due to appropriate acidity, boiling point of acid, and diffusion length. . However, from the viewpoint of the environment, such photoacid generators having a pF〇s-type perfluoroalkanesulfonyl structure have low flammability and are suspected to be bioaccumulating. A report issued by the U.S. Environmental Protection Agency entitled "Perfluorooctyl sulfonate; recommended important new use regulations (Perfluorooc: tyl SulfQnates;

Proposed Significant New Use Rule) proposes to regulate the use of these compounds. Therefore, in the field of microfabrication, it has been desired to develop an ingredient which is functionally excellent as a photoacid generator without such disadvantages. It is an object of the present invention to provide a novel photoacid generator which, when used as a photoacid generator which is sensitive to radiation or heat, to deep ultraviolet light such as KrF excimer laser, ArF excimer laser, F2 excimer Laser, or EUV, and electron beams exhibit high transparency, exhibit high flammability and are not bioaccumulative, and produce a high acidity, high boiling point, moderately short diffusion length in the photoresist coating, and a low correlation acid of a mask pattern density; a sulfonic acid produced by a photoacid generator; a sulfonic acid derivative useful as a raw material or intermediate of a synthetic photoacid generator; and a photoacid-containing product

1304060 V. INSTRUCTIONS (4) Positive or negative radiation-sensitive resin composition of the agent. SUMMARY OF THE INVENTION First, the present invention provides an acid generator (hereinafter referred to as "acid production (I)"), which comprises a compound represented by the following chemical formula (I) as "structure (I)") , Bu & Ζ1 R - C - S0. Z2 or a single group, a nitro group, a cyano group or a hydrogen atom wherein R represents a fluorine content of 50% by weight or less, and Zi and ζ2 are a straight or branched chain of 1 to 10 carbon atoms, respectively. Perfluoroalkyl. Next, the present invention provides a blue acid represented by the following chemical formula (丨-a) (hereinafter referred to as "sulfonic acid (Ia)"), and no stone yellow Z1 (I - a) - C - S0 Ζ2 wherein R represents a monovalent organic group having a fluorine content of 50% by weight or less, a nitro group, a cyano group, or a hydrogen atom, and z and 22 are each a fluorine atom or a straight chain or a branch having 1 to 10 carbon atoms; Chain perfluoroalkyl. Third, the present invention provides a sulfonic acid represented by the following chemical formula (1C)

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Salt (hereinafter referred to as "sulfonate (丨c)") z1 R — c — so3m (10

I z2 wherein R represents a monovalent organic group having a fluorine content of 50% by weight or less, a nitro group, a cyano group, or a hydrogen atom, and Z! and 22 are a fluorine atom or a straight chain or a branch having a carbon atom, respectively. Chain perfluoroalkyl, and μ is Na, κ /,

Li. In the fourth aspect, the present invention provides a sulfonium compound represented by the following chemical formula (4A) (hereinafter referred to as "sulfonium halide compound (4 A)"), Z1

I R — C — S02 A (4A)

I z2 wherein R represents a monovalent organic group having a fluorine content of 50% by weight or less, a nitro group, a cyano group, or a hydrogen atom, and Ζι and Z2 are each a fluorine atom or a linear chain having 1 to 10 carbon atoms or A branched chain perfluoroalkyl group, and A is a halogen atom. A fifth 'the present invention provides a positive-type radiation-sensitive resin composition comprising: (a) an acid generator (I), and (b) an alkali-soluble or alkali-soluble solution containing an acid cleavable group Resin, when the acid cleavable group dissociates, the resin becomes soluble in alkali.

1304060

A JL type radiation-sensitive resin composition, wherein '(b) an alkali-soluble resin, and (c) an alkali is dissolved. Sixth, the present invention provides: (a) an acid generator (I) degree control agent.勹f七/ The present invention provides a negative-type radiation-sensitive resin composition, which has a ?3 acid generator (1), (b) an alkali-soluble resin, and (c) a cross-linkable base which is soluble in the presence of an acid a compound of a resin. Other objects, features, and advantages of the present invention will be apparent from the description. The invention will now be described in more detail. _^1^ The present invention will now produce an acid generator (I) which generates an acid (I _ a) by heating with a specific example of acid, and is exposed when exposed. Or share 0. The acid generator (1) can produce an acid having a high acidity such as sulfonic acid or the like because of the presence of a strong fluorine-containing fluorene group in the ? to the sulfonate group in the structure (I). In addition, the acid produced is difficult to sublimate in the lithography process due to its high boiling point and it has a moderately short acid diffusion length in the photoresist coating. Further, the amount of fluorine in the acid is higher than that of the perfluoroalkane. The fluorine in the sulfonic acid has a low inside, and thus the flammability is relatively high, and its accumulation in the human body is low. =================================================================================================================== (R12), a S-R11, a SO-R11, an S02-R11 (wherein R11 and R12 represent a substituted or unsubstituted direct bond, a branch bond, or a ring unit price, respectively, having 3 carbon atoms a hydrocarbon group substituted with 6 to 3 carbon atoms or

1304060 V. DESCRIPTION OF THE INVENTION (7) Unsubstituted aryl group, or substituted or unsubstituted monovalent heterocyclic organic group having 4 to 30 carbon atoms) and the like. Examples of the unsubstituted linear, branched or cyclic monovalent hydrocarbon group having 30 carbon atoms of R11 and R12 include a mercapto group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, and the like. Tributyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, isooctyl, 2-ethylhexyl, n-dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, with a group of a terpene structure, a group having a norylene structure, a group having a tricyclodecane structure, a group having a tetracyclododecane structure, or the like. As examples of the substituent of the above hydrocarbon group, an aryl group, an alkenyl group, an organic group containing a hetero atom such as a halogen, oxygen, nitrogen, sulfur, phosphorus, ruthenium or the like can be given. Examples of the linear, branched or cyclic monovalent hydrocarbon group having 30 carbon atoms substituted by the above substituents include a benzyl group, a fluorenyloxymethyl group, a methylthiomethyl group, an ethoxylated group, and a benzene group. Oxymethyl, oxacarbonylmethyl, ethoxycarbonyl, ethyl fluorenyl, fluoromethyl, trifluoromethyl, chloromethyl, trichloromethyl, 2-fluoropropyl, trifluoroacetam Base, trichloroethenyl, pentafluorobenzhydrylmethyl, amidoxime, cyclohexylamine decyl, diphenylphosphinium decyl, tridecyl fluorenyl, 2-phenylethyl, 3-phenylpropyl And 2-aminoethyl. Examples of the unsubstituted aryl group having 6 to 30 carbon atoms of R11 and R12 include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-onion group, a 1-phenylidene group and the like. Examples of the monovalent heterocyclic organic group having 4 to 30 carbon atoms of R11 and R12 include a coughyl group, a σ-sepeno group, a fox thiol group, an oxime group, a phenanthrene group, and a valenyl group. , sigh σ sitting base, different called σ sitting base, ρ than base, cancer bite base, tower σ 丼 base and so on.

C:\2D-CODE\91-09\91114303.ptd Page 12 1304060 V. INSTRUCTIONS (8) Examples of substituents of a fluorenyl group and a monovalent heterocyclic organic group: methane & An organic group containing a hetero atom such as dentate, oxygen, nitrogen, sulfur, phosphorus, ruthenium or the like. —: Examples of the substituted aryl group having 6 to 30 carbon atoms include an o-quinone group, a m-tolyl group, a p-fluorenylphenyl group, a p-methoxyphenyl group, and a 2,4,6-trimethylbenzene f. , o-isopropylphenyl, 2'3-dimethylphenyl, p-fluorophenyl, p-trifluoromethylphenyl, p-bromophenyl, p-chlorophenyl, p-iodophenyl and the like. Examples of the substituted monovalent heterocyclic organic group having 4 to 30 carbon atoms are exemplified by 2-bromocarbyl and 3-methoxy. Sequim and so on. With respect to the group R in the formula (I), a hydrocarbon group such as methyl group, ethyl '5 butyl group, cyclohexyl group, phenyl xiaocayl group, and having a dehydrogenate, deuterium, and di-nonanecane may be mentioned. a structure, or a group of a tetracyclododecane structure, and a group -S-R11, -SO-R11, and -S02-Ru (wherein a Ru-based hydrocarbon group such as anthracenyl, tert-ethyl, n-butyl, cyclohexyl Or a phenyl group, particularly preferably a group having a structure of nortenyl, dilute, deuterium or tetracyclododecane. Examples of the all-burning group having 10 carbon atoms of oxime 1 and oxime 2 in the chemical formula (I) include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, a Nine-Nong-butyl group, and the like. Wait. The preferred structure of the soil (I) is exemplified by the following chemical formulas (丨-丨), (I-2), and (I-3), and (I-1) and (1 to 3) are particularly preferred. .

F 1-1 C —S 0〇

F

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C:\2D-OODE\91-O9\9in4303.ptd Page 14 1304060 V. Inventive Note (ίο) Valence group, R' represents a monovalent substituent, k is an integer of 0 or more, and η is 0-5 The integer. Examples of the divalent group of oxime 1 include -0-, -S-, carbonyl, sulfinyl, sulfonyl, fluorenylene, 1,1 -ethyl, 1,2 - Base, propyl, 1-mercaptopropyl, 1-ethylpropyl, tri-indenyl, difluoroindenyl, tetrafluoro-1,2-extended ethyl, 1,2-phenyl, 1 , 3-phenylene, 1,4-phenylene, and the like. Among these divalent groups, a carbonyl group, an anthranylene group, a difluoroindenylene group, and a tetra-l-,2-diethyl group are preferred. Examples of the monovalent or divalent substituent of R' include a keto group (=0), a hydroxyl group, a carboxyl group, a fluorenyl group, a linear or branched alkyl group having 10 carbon atoms, and 1-10. a straight or branched chain vinylidene group of carbon atoms, a monovalent cyclic organic group having 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, a linear or branched chain having 1 to 10 carbon atoms Alkoxy group, aryloxy group having 6 to 20 carbon atoms, linear or branched alkanecarbonyl group having 2 to 10 carbon atoms, aromatic carbonyl group having 7 to 20 carbon atoms, having 10 carbon atoms A linear or branched alkoxycarbonyl group, an aryloxycarbonyl group having 7 to 20 carbon atoms, and the like. Examples of straight or branched alkyl groups having 10 carbon atoms are anthracenyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-glycol. Base, n-octyl, n-decyl, n-butyl and the like. Examples of straight or branched chain vinylidene groups having 10 carbon atoms are an anthracenylene group, a vinylidene group, a propenylene group, a 1-decenylene group, and a 1-ethylpropylene group. and many more. An example of a monovalent cyclic organic group having 1 to 1 carbon atoms is a cyclopentyl group and a ring.

C:\2D-OODE\91-O9\91114303.ptd Page 15 1304060 V. INSTRUCTIONS (11) Hexyl, adamantyl, n-radical, camphordiyl and the like. Examples of the aryl group having 6 to 20 carbon atoms are phenyl, o-phenylphenyl, m-phenylene, p-nonylphenyl, p-hydroxyphenyl, 1-naphthyl, 1-onionyl, benzyl, etc. Wait. Examples of straight or branched alkoxy groups having 1 to 10 carbon atoms are an anthraceneoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a third butoxy group, and the like. . Examples of the aryloxy group having 6 to 20 carbon atoms are a phenoxy group, a p-hydroxyphenoxy group, an o-tolyloxy group, an m-tolyloxy group, a p-tolyloxy group and the like. Examples of the linear or branched alkanecarbonyl group having 2 to 10 carbon atoms are a fluorenylcarbonyl group, an ethylcarbonyl group, a n-propylcarbonyl group, an isopropylcarbonyl group, a n-butylcarbonyl group, a tert-butylcarbonyl group and the like. Examples of the arylcarbonyl group having 7 to 20 carbon atoms are a phenylcarbonyl group, a fluorenylcarbonyl group and the like. Examples of straight-chain or branched-chain alkoxycarbonyl groups having 2 to 10 carbon atoms are methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl, and the like. . Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms are a phenoxycarbonyl group, a benzyloxycarbonyl group and the like. These substituents may have any substituent, for example, one or more of the foregoing substituents. In the chemical formulas (Ι-A) and (I-B), R' may be bonded to any carbon atom forming a deinsenic ring or a deuterium ring. If two or more R' groups are present, they may be the same or different. In the chemical formulas (Ι-A) and (I-B), Y1 is a single bond, a methylene group, or a carbonyl group.

C:\2D-CODE\91-09\91114303.ptd Page 16 1304060 V. Description of the Invention (12) Preferably, k is preferably 0, and η is 0 or 1 is preferred. Examples of preferred structures of (I - A ) and (I - Β) include the following chemical formulas (A-1) to (A-12) to (B-12).

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C: \2D-C0DE\9]-09\91114303.ptd Page 21 1304060 V. Description of Invention (17) Regarding the ionic compound of the acid generator (I), the following chemical formula (I) A salt compound (hereinafter referred to as "silk] sulfonate compound (1)"). The sulfonate compound (1) is a compound in which a sulfonyl group of the structure (I) is bonded to an oxygen anion to form a sulfonic acid anion. Z]

I R —C —S 〇3~ M+ (1 )

I z2 In the chemical formula (1), R'Z1 and Z2 have the same definitions as the chemical formula (I), and M+ is a monovalent cation. Examples of the monovalent iron cation of M+ include 0, S, Se, N, P, As, Sb, C1, Br, 1, and the like. Among these <silver cations, S and I are preferred. In the chemical formula (1), examples of the monovalent stable cation represented by M+ include the following chemical formulas (i) and (i i ): R1

I R2 —S+ —R3 ( i ) wherein R 1 , R 2 , and R 3 represent a substituted or unsubstituted, straight or branched alkyl group having 20 carbon atoms, respectively, having 6 to 20 carbon atoms. a substituted or unsubstituted aryl group, or two or more of R1, R2, and R3 together with a sulfur atom in the formula form a ring, and R4 - V - R5 (ii)

C:\2D-CODE\91-09\91114303.ptd Page 22 1304060 V. Inventive Note (18), wherein R4 and R5 represent substituted or unsubstituted, linear chains having 1 - 2 carbon atoms, respectively Or a branched alkyl group, or a substituted or unsubstituted, substituted 6-20 carbon atom, a group, or a P and a hydrazine form a ring together with a filled atom in the formula. The monovalent pin cationic group of Μ+ can utilize the known formula &, for example, p' "J. V - 110' progress in polymer science (-es; η

Lyme~. The method of enc° 62, 49, 1 984 is produced. Examples of the preferred cations of the cations include the cations of η (4)* and the phosphonium cations represented by the following chemical formula (1) = (11-39). "

CH3 (i - 2) (i -1)

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C:\2D-CODE\91-09\9m4303.ptd Page 31 1304060 V. Description of invention (27) H3c-s1-<^ 》(i-37) Λ H3C- )〉(i-38) H3C - S— )/—OH (i-39) ch3 h3c-s1ch3 (i-40) ch2ci H3. - > (i-41) ch3 , _, H3C — stcH2C〇-^〇> (i -42)

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(i-54) (i-55) (i-56) (i-57)

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•〇CH2C〇OC(CH3)3 (ii - 28)

〇 '•Ky>-〇-c 〇一C—〇—C(CH3)3 (ii-29)

CH3OOC

0C(CH3)3 (ii - 30) COOCH3 (ii-31) COOCH3 (ii-32)

CH300C (CH3)3COOCCH2〇 〇CH2COOC(CH3)3 (ii-33)

〇〇(CH3)3C-〇-C-〇o each oc(ch3)3 (CH3)3CO 〇C(CH3)3 (ii-34) (ii-35) 11_画_1 C: \2D-mDE \91 -09\91114303 .ptd Page 41 1304060 V. Description of invention (37)

(ii-36) (ii-37)

(ii-38)

(ii - 39)

C:\2D-CODE\91-09\91114303.ptd Page 42 1304060 V. Description of Invention (38) Among these monovalent II cations, from the chemical formula (i-1), (i-2), (Bu 6 ), (i-8), (i-13), (i-19), (i-25), (i-27), (i-29), (i-51), and (i-54) The read cations shown, and the lock cations represented by the chemical formulas (ii-1) and (ii-11) are preferred. As the preferred sulfonate compound (1), a compound of the following chemical formula (A) or (B) can be mentioned.

(1-A)

M+ (1HB) wherein Z1 and Z2 are as defined in formula (I), Yl, R', k, and η are as defined in formulas (I - A) and (I - Β), and Μ + are as in formula ( 1) Defined. The nonionic compound of the acid generator (I) may, for example, be an N-sulfonyloxyquinone imine compound of the following chemical formula (2) (hereinafter referred to as "N-sulfonyloxyphthalimide compound (2)) "). t Z1 Y彳 R—C—S02-0

(2)

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Wherein R, Z], and Z2 are, for example, a chemical hydrogen atom or a substituted or unsubstituted singular 'R6 and 1^7, respectively, representing a carbon atom bonded to a group R6 or R7, or R6, respectively. And R7 may form a ring with a double bond 'or a divalent organic group #, and Y2 is a single bond, and the compound of the above formula (2-Α) or (2-Β) with respect to the oxime-sulfonyloxy quinone imine compound (1) Compound. Give

:R'\ Ζ1 -Y1-c—

S〇2〇—N

(2-A)

R6 R7 (2 - B) R, k, and n are as in the chemical formula, and Ζ 1 and Ζ 2 are as defined by the chemical formula (I), and the γ 1 chemical formula (Ι-Α) and (Ι-Β) are defined. , and R6, R7 (2) are defined. The preferred quinone imine group bonded to the sulfomethoxy group (s〇_〇_) of the chemical formula (2), (2-A) or (2_B) may be exemplified by the following chemical formula (2d) to 2

1304060

5. The description of the invention (40) (2-9).

〇

〇

Ο

(2-5)

(2-6)

Among these quinone imine groups, a group of the formula (2-1), (2_4), (2-8), or (2-9) is preferred. A method of producing the oxime sulfonate compound (1) will now be described in detail. The 13⁄4 acid salt compound (1) can use a known method such as]).D d e s

Marteau (inorganic chemistry, Vol. 32, 50 0 7, 1 993) or factory fire (: 1^"11〇 (Polymers' 62, 49, 1984). (1) by reacting a precursor (1 a) with a dithiazide SI salt compound to produce a ylide acid salt (lb), using a succinic acid = gasification in the presence of an inorganic test, such as a gasification Expecting to oxidize the sub-acid salt (1 b) to produce a sulfonate (丨, , , and then use the opposite meaning

1304060 V. INSTRUCTIONS (41) The sub-exchange precursor Μ+Γ is subjected to an ion exchange reaction to obtain a reaction formula (1) ζ1 Z1 R- έ—[la] ΝΒ2^2〇4 R~^S〇2Na 21 L· R-9-S03Na Z Z2 [lb] "Ί [lc] , 21 R-έ-S〇3 M+ (1) Ζ2 where X is a releasable monovalent group' and a t-unitary anion. About the precursor (1 a) Examples of the liberable monovalent group of X include, in addition to a tooth atom such as chlorine, bromine, and iodine, a mesylate group, a sulfonate group, and the like, and a bromine and iodine atom are preferred. In the reaction of the precursor (la) with dithiocarbamate, the molar ratio of the two pairs of precursors (la) is usually 0.01_1 〇〇, and preferably 10 0 0. About the use in the reaction. Examples of inorganic bases, sodium, potassium carbonate, lithium hydrogencarbonate, sodium hydrogencarbonate, carbonium, sodium hydrogencarbonate and potassium hydrogencarbonate are preferred. 氕Katsiji Temple, and an inorganic base to sodium dithiosulfinate It is preferably 2· 0-4· 0. ϋ 10· 0 ^ The reaction is an organic solvent in a mixed solvent of an organic solvent and water, and it can be mentioned that the water is high in the order of the water. Mutual solubility Eighty-four lice furan, N, N~ dimethylformamide Sa w N1 low \ alcohol, A storm methylamine, N, N- dimethylacetamide, hexyl

C: \2D-GODE\91-09\91114303.ptd Page 46 1304060 V. Description of the invention (42) Nitrile, disulfoxide, etc. are preferred examples, with N,N-dimethyletheneamine, Acetonitrile and diterpene are harder, and acetonitrile is particularly preferred. The organic solvent is usually used in an amount of from 5 to 100 parts by weight based on 100 parts by weight of the total amount of the organic solvent and water, preferably from ίο-loo by weight, and particularly preferably from 2 to 9 parts by weight. The reaction is carried out usually at a temperature of usually from 40 to 200 ° C and at a temperature of from 60 to 1 20 ° C for usually from 0.5 to 7.2 hours, and preferably from 2 to 24 hours. If the ruthenium temperature used is higher than the boiling point of the organic solvent or water, a pressure vessel such as a hot press dad is used. As the oxidizing agent used in the oxidation reaction of the sulfinate (1b), in addition to hydrogen peroxide, hemi-perbenzoic acid, t-butyl hydroperoxide, potassium peroxysulfate, and the like may be mentioned. Potassium manganate, sodium perborate, sodium metamorphic acid, chromic acid, sodium dichromate, ii, dichlorobenzene, diphenyl acetic acid, cerium oxide (VII), cerium oxide (V11), sodium hypocarbonate Sodium chlorite, oxygen, ozone gas, etc., preferably hydrogen peroxide, chloroperbenzoic acid, and tert-butyl hydroperoxide. The molar ratio of the oxidizing agent to the sulfinate (lb) is usually from 1.0 to 10 Torr, and preferably from 1 to 5 - 4 · 0. Further, a transition metal catalyst can be used together with the aforementioned oxidizing agent. Examples of the transition metal catalyst include disodium tungstate, iron chloride (Π I), gasified ruthenium (I II), and selenium oxide (1 V), and disodium tungstate is preferred. The molar ratio of the transition metal catalyst to the sulfinate (1 b ) is usually 〇. 〇〇J - 2 · 0, with 0 · (Π -1 · 〇 preferably, and 〇 · 〇 3 - 〇 · 5 Very good.

Page 47 1304060 V. INSTRUCTIONS (43) In addition to the foregoing: oxidant and transition metal catalyst, a graded granule can be used to control the pH of the reaction solution. = Examples of retarding agents: exemplified by disodium hydrogen phosphate, dichlorophosphate, potassium dipotassium silicate, etc. 'buffering agent to sub-item salt (the j-ear ratio is usually 〇.〇卜2.〇 Preferably, it is 0.03 M.0, and m 隹0, and the reaction is usually carried out in a reaction solvent. Examples of the reaction solvent include water, an organic solvent such as lower alcohol, tetrahydroanthracene, and n, n. _ dimethylformamide: n, n-dimethylacetamide, acetonitrile, dimethyl sulphate, acetic acid, trifluoroacetic acid, etc., as a preferred example, with methanol, N, N_: methyl acetamide It is better to use it, and it is better to use it. It is especially good for decyl alcohol. For the sulfinate (ib) with a weight of 1 and the reaction solvent, the amount of the reaction solvent is usually 5 100, and the weight is 1 10 - 1 part by weight is preferred, and the part by weight is particularly good. If necessary, the above organic solvent can be used together with water. In this case, the organic solvent is usually used in an amount of 5 - 1 part by weight, 1〇_1 parts by weight is preferred, and 20-90 parts by weight is particularly good. The reaction system is usually 0-10 (rc, with 5-6 (rc is preferred, and 5-4 (rc excellent temperature) Under the usual 〇·5—72 hours, and 2 Preferably, 24 hours is used. The ion exchange reaction of the sulfonate (lc) can be carried out by a known method, for example, as described in "j. ν·Crivel 1〇, Progress in Polymer Science 62, 49, 1 9 8 4". A method such as ion exchange chromatography can be used in the ion exchange reaction described in the above. For the example of the monovalent anion in the reaction formula (1), F_

C:\2D-CODE\91-09\91114303.ptd Page 48 1304060 V. INSTRUCTIONS (44) C1, Β Γ P, gas radicals, hydrogen sulfate, acid dihydrogen, tetrafolate , aliphatic sulfonate, aromatic sulfonate, triflate, gas acid, hexafluoride phosphate, hexachloroantimonate, etc., with, hydrogen sulfate, tetrafluoroborate, and lipid The sulfonate group is preferred, and C 1 , β r , and hydrogen sulfate are particularly preferred. The molar ratio of the opposite ion exchange precursor to the sulphate (lc) is usually 〇1 -1〇, preferably 〇3 - 4 ,, and 〇 · 7 - 2 · 0 is particularly preferred. This reaction is usually carried out in a reaction solvent. As the reaction solvent, water, an organic solvent such as lower alcohol, tetrahydrofuran, N,N-didecylguanamine, N,N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, etc. may be mentioned. In good cases, it is better to use water sterol, N,N-dimercaptoacetamide, residual, and bismuth stone, and water is particularly good. 3 pairs of 100% of the weight of the opposite ion exchange precursor, the amount of the reaction solvent = often 5 to 100 parts by weight, preferably 1 〇 1 〇〇 part by weight, and 2 〇 _ 5 parts by weight good. If necessary, water can be used together with organic solvents. In the case of a denier, the total amount of the organic solvent and water is 0 parts by weight, and the organic solvent is used in an amount of 5 - 1 part by weight, preferably 1 part by weight. The 1U" knife weight is better, and 2. The reaction is usually in the range of 0-80 t, preferably 5-30 〇C, θ 1 〇 minutes to 6 hours, and 3 minutes to 2 hours. It is purified by solvent extraction using a sulfonate compound (丨) which is usually obtained in this manner. i is preferably mixed with water by using an organic solvent for purification, and examples thereof include esters such as ethyl acetate and ethyl acetate. Bath sword is a butyl ester, ether such as B

Page 49 1304060 V. INSTRUCTIONS (45) ----------- Keys and halogenated alkyl groups such as dioxane and gas imitation. The sulfonate compound (丨) is a compound of the formula (1 - A) via a dilute derivative (10) (the selastyl derivative (2a) and the cyclopentadiene compound) according to the following reaction formula (2) Dijon _ Adel (diels_M should be prepared), or normethene derivative (3b) (which is derived from cyclopentadienyl and demethylated olefins prepared in reaction formula (3) The Diershikou-Adel reaction of the substance (2b) is obtained according to the reaction formula (。). The terminal acid salt compound (1) having three or more dedecene or deuterium ring can be obtained. The polycyclodecanthene derivative is synthesized by repeating the steps shown in the reaction formula (3), and then obtained according to the aforementioned steps. Reaction formula (2) Ο Z1 CHg-CH γΐ-C~X Ζ2 [2a] Di Earshiel-Adel reaction Z1

Y1—C—X i2

[2b] In the reaction formula (2), the Z1 and Ζ2 systems are the same as defined in the chemical formula (I), and the Y1 system is the same as defined in the chemical formulas (I - A) and (I _ B), and the X system and the reaction The definitions in the formula (1) are the same. Reaction formula (3)

C: \2D-C0DE\9 Bu 〇9\911H303 .ptd Page 50 1304060 V. Description of invention (46)

〇 [2b]

Dimes-Adel reaction In the reaction formula (3), the Z1 and Z2 systems are the same as defined in the chemical formula (I), the Y1 system is the same as defined in the chemical formulas (I_A) and (IB), and the X system and the reaction are The definitions in the formula (1) are the same. The reaction formulas (2) and (3) will now be described in more detail. With regard to the Dier-Adel reaction in the reaction formulas (2) and (3), a known method can be used, such as the description in "Comprehensive Organic Synthesis", Β·Μ·Trost & I. Fleming , Pergamon Press, New York, 1991, Vol. V, p. 315. When the Dimes-Alder reaction is carried out, the molar ratio of the ethylene derivative (2a) to the cyclopentadiene compound and the molar ratio of the cyclopentadiene compound to the decanted dilute 1 (2b) are usually 〇 · (π-loo, and 〇·卜1〇. This reaction can be carried out in the absence of a solvent, or in a reaction solvent such as hydrazine, N,N-dimethylformamide, tetrahydrofuran, 1,2 - dichloroethane ~ etc. - alkane, etc.

Η C:\2D-00DE\91-09\91114303.ptd Page 51 1304060 V. INSTRUCTIONS (47) -- The reaction system is usually 2 0 - 2 5 0 °C, 8 〇 - 1 80 ° ° C is preferably at a temperature of usually 0. 5 - 2 4 hours and preferably 4 - 12 hours. If the temperature of the reverse 2 used is higher than the boiling point of the reaction starting material or the reaction solvent, a pressure vessel $ such as an autoclave is used. The oxime sulfonate compound (1) represented by the formula (1-B) can be obtained by subjecting a normethene derivative (for example, a dealkylene obtained by the reaction formula (2) or (3)). The derivative (2b) or (3b)) is obtained by contacting hydrogen with a reaction solvent in the presence of a hydrogenation catalyst hydrazine. η Examples of the hydrogenation catalyst include transition metal catalysts such as Raney nickel, palladium-carbon, platinum oxide (ιν), ruthenium-carbon, ruthenium-alumina, ruthenium-carbon, gins-(triphenylene). Phosphine) Chloroquinone (丨;) and so on. The weight ratio of the transition metal catalyst to each de-throkenne derivative is usually 〇 0 0 1 - 1 ' and Q · 〇 1 - 〇 . 2 is preferred. The hydrogen pressure during the hydrogenation reaction is usually 120 ° C, preferably 1 - 丨〇 〇 at atmospheric pressure, and particularly preferably 1 - 50 atm. This reaction is usually carried out in a reaction solvent. As the example of the reaction solvent, an organic solvent such as methanol, ethanol, ethyl acetate, toluene, diphenylbenzene, tetrahydrofuran, 1,2-dichloroethane or the like can be given. The weight ratio of the reaction solvent to each nordecene derivative is usually 丨-丨〇 〇, preferably 5 - 1 〇 ,, and 1 〇 -8 〇. The reaction is carried out at a temperature of usually 20-20 ° C, preferably 20-150 ° C, and preferably 20-100 ° C, usually at 〇 5 _ 24 hours, and preferably at 4 - 12 hours. . If the reaction temperature used is higher than the boiling point of the reaction raw material or the reaction solvent or if the pressure of the hydrogen used exceeds 1 atm, the pressure vessels are used.

C:\2D-CODE\91-09\91]14303 .ptd Page 52 1304060 V. Description of the invention (48^ ~ " ' -- such as hot pressure dad. Next, the N-sulfonyl oxonium will be described in detail. The method for producing the imine compound (2). The π N-and the fluorenyl oxyimide compound (2) is, for example, a sulfinate (丨b) or a sulfonate represented by the reaction formula (1).丨c). Specifically, as shown in the following reaction formula (4), a sulfonate (1 b ) is converted into a sulfonium halide compound (4 A) such as sulfonium using a halogenating agent such as chlorine gas. Chlorine (4a) ° The reaction of the sulfonium halide compound (4A) with the oxonium imine compound in the presence of a catalyst in the presence of a catalyst to produce an N-sulfonyloxyquinone compound (2) 〇 Reaction formula (4) )

Regarding the reaction of the sulfinate (1b) with a chlorinating agent, a known method such as those described in "D. D. DesMarteau, Inorganic Chemistry, Vol. 32,

C: \2D-CODE\91-09\91114303.ptd Page 53 1304060

5. Description of the Invention (49) The method of 5 1 0 7,1 9 9 3" or the method described later in the synthesis example. In U.S., the method of foaming the gas into the reaction solution is called gasification in which a larger excess amount of the sulfonate (lb) is usually used in the reaction. This reaction is usually carried out in a reaction solvent. With respect to the reaction solvent, effluent, organic solvent such as tetrahydrofuran, N,N-dimethylformamide, N,/monomethyl decylamine, [nitrile dimethyl benzoate, etc. are preferred hydrazines N: Dimethyl ethanoamine, ... and dimethyl ya ... good and good: 〇〇 part by weight of the acid salt (lb), the reaction solvent is usually used in an amount of 5-1 〇〇 weight, in parts by weight Preferably, and 2 〇 5 parts by weight. If necessary, the aforementioned organic solvent can be used together with water. In this case, the amount of water and the total amount of organic solvent used in the 'organic solvent' is 5-1 parts by weight, preferably 1〇_1 parts by weight, and 2〇_9〇. The weight is very good. The reaction system is usually carried out at a temperature of usually 0 to 10 (TC, preferably 5 to 6 (rc is preferred, and 5 to 4 Torr), usually 5 minutes to 12 hours, and preferably 1 minute to 5 hours. 4a) In the reaction with the N-hydroxyindole imine compound, the molar ratio of the N-hydroxyquinone imine compound to the sulfonium gas (4a) is usually 〇. 〇〇1〇〇, 〇·3-5. 0佳,和〇· 5_2· 〇特佳. · This reaction is usually carried out in a reaction solvent.

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Ethyl acetonitrile, decyl decylamine, tetrahydrofuran-sulfoximine, dioxane, acetonitrile, tetrahydrofuran, alkane/odorane, and gas imitation are preferred examples and a gas-fired gas is particularly preferred. = 00 parts by weight of sulfonium chloride (4a), the reaction is 5 - 100 parts by weight |, ! η , Λ Λ is usually preferred. Preferably, it is preferably from 1 〇 to 100 parts by weight, and from 20 to 50 parts by weight, with respect to the catalyst, virgin, 2,6-dimethyl 17 to π and one-lead bicycloundecene. Triethylamine, pyridinium, anthracene, and quinone-diethylaniline are preferred examples, and the ratio of triterpene, hydrazine, hydrazine-diisopropylethyl 4-methylamine to tl, ethylamine and The molar ratio of 4-diaminoguanidine oxime to the sulfonium chloride (4a) as a base catalyst is usually 丨.1 - 5 - 5 · 0 is preferred, and 1 · 5 - 3. 0 is particularly preferred. · Reaction to the end 8 (rc, 5 to 3 (the preferred temperature for rc is 2 to 6 hours, and preferably 1 to 2 hours. Chemical formula (2-A) or (2-B) N-sulfonyloxyindolamine compound (by the step shown in the reaction formula (1), from the demethylated article: the deuterated derivative (2b) or (3b) or previously related to the chemical formula ( 1 _A) or (1-B) oxime sulfonate compound (1) is prepared by the gasification derivative thereof to prepare a sulfinate (lb), and then according to the reaction formula (4) ^ step ^ Further, as an example of the acid generator (I) other than the oxime sulfonate compound (1) and the N-renewed oxynitride compound (2), a sulfone compound and a sulfonic acid δ can be cited. A compound, a diterpenoid-based diazonium-containing compound, a bismuth-based sulfonate compound, a sulfonium sulfonate compound, a sulfonium sulfonate compound, and the like.

C:\2D-C0DE\91-09\9lll4303.ptd Page 55 1304060 V. INSTRUCTIONS (51) These compounds will now be discussed. Examples of the ruthenium compound include a 5-ketosulfone, a /5-sulfonylsulfone, and an α-diazonium compound of such a compound.

〇Ζ1 II IC-S〇2-C-R Ζ1 | Ζ1 IC-S〇2—CHo—S〇2 CR z2 Clear examples of sulfone compounds include compounds of the following chemical formulas (3 - 1) and (3 - 2): (3-1) (3 - 2) wherein R, Z1, and Z2 are the same as defined in the formula (I), and the two R'Z1 and Z2 groups in the formula (3-2) are the same or different. Examples of the acid-reducing compound include a sour acid-steaming method, a sulphuric acid-steaming vinegar, a sulphuric acid sulphuric acid, and a resorcinimide S. A clear example of the rhein _ compound includes the compound of the following chemical formula (4)··

C:\2D-CODE\91-09\91114303.ptd Page 56 1304060 V. INSTRUCTIONS (52) wherein R, Z1, and Z2 are the same as defined in chemical formula (I), when there are two or more R In the case of the Zi, and Z2 groups, these groups may be the same or different; A represents a j-valent organic residue derived from gallicol, α-hydroxydecyl benzoin or the like; and j is an integer of 3 . As an example of the disulfonyl diazonium compound, a compound of the following chemical formula (5): Z1 Z1

R-C-S〇2-C-S〇2-C-R

Wherein R, Z1, and Z2 are the same as defined in the formula (I), and the two R, Z1, and Z2 groups are the same or different. As an example of the disulfonyl decane compound, a compound of the following chemical formula (6): Z1IR-C-S〇2* VI ~C-S〇2* w

Z1 I•C—R

Wherein R, Z1, and Z2 are the same as defined in the chemical formula (I), and two R,

C:\2D-CODE\91-09\91114303.ptd Page 57 1304060

V. INSTRUCTIONS (53) The Z1 and Z2 groups are the same or different; v and w represent a flavonoid, linear or branched monovalent aliphatic hydrocarbon group, respectively, or have a heterogeneous* hydrogenogen group, the limitation The condition is that at least one of V or a circle is a ary meaning, the unit price of which is combined to form a monocyclic or polycyclic ring 1 containing at least one unsaturated bond, or V and w can be a group of formula (7): °苒, Or below

(7) wherein V' and W' each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or an aryl group, or each of the same or different carbon atoms is bonded to a bismuth, which combines to form a monocyclic carbon structure, and a An integer from 2 to 1 〇. Examples of the sulfonium sulfonate compound include the following compounds of the chemical oxime (8-2): ή dry type (8-〇 or R8 Ζ1 (8-1)

NC—C=N—〇—S〇29—R f R9 21 I ii R—S〇2—0—N=C—C=N 一〇—S〇2—c~r (8—2) Z2 R9 22 wherein R, Z1, and Z2 are the same as defined in the formula (I), and the two R, Z1, and ζ2 groups in the formula (8-2) are the same or different, and r8 and r9 represent a monovalent organic group, respectively. Group.

C:\2D-CODE\9I-09\91114303.ptd Page 58 1304060 V. Inventive Note (54) or (9-2) Compound: Z1

I (9-1)

R—〒一s〇2~NH—NH: F f1 Z1 R—c-so2—nh-nh-so2—CR (9-2) Z2 z2 where R, Z1, and z2 are related to the chemical formula (T, (9) -2) The two R, Z1, & Z2 groups # ^ have the same definition, the chemical heart and the turbulence group are the same or different. The de-radiation sensitive, shame-salt compound composition into a positive 3 radiation sensitive resin The composition includes the following composition of composition - C1) (a) acid production peak Hao Hao μ, ^ / ~ 夂 生 d (), and (b) resin containing acid cleavable = insoluble or almost Insoluble in alkali, A becomes soluble in alkali when the acid cleavable group is decomposed (hereinafter referred to as "resin containing acid-cleavable group") (hereinafter referred to as "positive type radiation-sensitive resin composition" ))); or (ii) (a) acid generator (I), (c) soluble resin, and (d) alkali dissolution control

Formulation (hereinafter referred to as "positive type radiation sensitive resin composition (ii)"). I It is preferred to use an acid generator (I) in the positive-type radiation-sensitive resin composition, and an acid generator having thermal and chemical stability. The positive type radiation sensitive resin composition (i) and the positive type radiation sensitive resin composition (i i ) of the present invention will now be described. In positive-type radiation-sensitive resin composition (i) and positive-type radiation-sensitive tree

C:\2D-〇〇de\91-09\91114303 .ptd Page 59 1304060 The resin or base of the acid generating agent used for the acid-generating resin i) is 0 · 1 - 15 parts by weight ( I) is less than 0. If more than 20 parts of the resin having reduced heat are related to the positive resin, the base and the alcoholic hydroxyl group become soluble in one or more of them. The group of the group of the acid-containing agent (I) may be used singly or in combination with both or in accordance with the invention (55) of the lipid composition (ii). For use in a positive-type cationic resin composition (i or other acid-containing cleavable group if necessary): .1 - 20 parts by weight, preferably. If the acid generator is expected to have an effect; pattern shape, and acid resistance The group of the cleavage-type radiation-sensitive resin may be a resin which may be substituted by a resin containing one or a base or a carboxyl group, and which is insoluble or almost insoluble in alkali-base resin by an acid cleavable group. When developing under the photoresist coating layer including the acid-containing cleavable substrate, if the thickness of the starting film is developed, the characteristic of the grease is referred to as "the composition (i) of the resin which does not dissolve the acid cleavable group and The amount of the positive radiation sensitizer (I) varies depending on the type of the acid generator (I). The resin is soluble in 1 part by weight, and the amount is usually preferably in an amount of from 0 to 2 - 12 parts. Weight • 1 part by weight, it is difficult to obtain the weight of the hair, the transparency and tendency of radiation. The acid-containing cleavable group of the product (i) contains a plurality of oxygen-containing functional groups such as the test through the presence of acid Dissociated from the hydrogen atom in the oxygen-containing functional group, and when the acid is cleaved The photoresist coating made of the resin in the dissociation of the group remains after 50% or more of the photoresist having the same positive light-sensitive sensitivity as the photoresist pattern of the resin of the group. An acid-containing cleavable or almost insoluble base. An example of a cleavable group in an acid,

C:\2D-OODE\91-O9\91114303.ptd Page 60 1304060 V. Description of Invention (56) A substituted thiol group, a 1-substituted ethyl group, a 1-substituted n-propyl group, and a branched branch are mentioned. A chain alkyl group, a calcined group, a styryl group, a pyrolyzed group, a sulfhydryl group, a cyclic acid cleavable group, and the like. Examples of the substituted methyl group include a methoxy group, a methylthiomethyl group, an ethoxylated group, an ethylthiomethyl group, a methoxyethoxymethyl group, an anthracene group, an anthracene group, and a benzoquinone group. Sulfhydryl, 4-bromophenylhydrazino, 4-oxobenzoylmethyl, 4-methylthiophenyl, α-mercaptobenzylidenemethyl, cyclopropylindenyl, benzyl Base, diphenyl fluorenyl, trityl, adamantyl fluorenyl, 4-bromobenzyl, 4-nitrobenzyl, 4-nonyloxyindolyl, 4-indolethiobenzyl, 4-ethoxybenzyl, 4-ethylthiobenzyl, piperonyl, anthranilylcarbonyl, ethoxycarbonylcarbonyl, n-propoxycarbonylhydrazino, isopropoxycarbonylhydrazino, n-butoxycarbonylhydrazino, tert-butoxycarbonylindolyl and many more. Examples of the substituted ethyl group include 1-oxooxyethyl group, 1-pyridylthioethyl group, 1,1-dioxaxyethyl group, 1-ethoxyethyl group, and 1-ethylthioethyl group. 1,1-diethoxyethyl, 1-phenoxyethyl, 1-phenylthioethyl, 1,1-diphenoxyethyl, 1-octyloxyethyl, 1-arylthioethyl, 1_ Cyclopropoxyethyl, 1-cyclohexyloxyethyl, 1-phenylethyl, 1,1-diphenylethyl, 1-methoxypolyethyl, 1-ethoxycarbonylethyl, 1-n-propoxy Carboxyethyl, 1-isopropyloxycarbonylethyl, 1-n-butoxycarbonylethyl, 1-tert-butoxycarbonylethyl, 1-cyclohexyloxycarbonylethyl and the like. Examples of the 1-substituted n-propyl group include 1-nonoxyn n-propyl group, 1-ethoxyethoxypropyl group, and the like. Examples of the 1-branched alkyl group include an isopropyl group, a second butyl group, a third butyl group, a 1,1-dimercaptopropyl group, a 1-methylbutyl group, and a 1,1-difluorene group. Butyl and the like.

C:\2D-CODE\91-09\91114303.ptd Page 61 1304060 Base Example Ethyl decyl decyl tributyl phenyl sulfonyl acetonyl group Examples of three butyl groups, glutinous aryl base, sulfhydryl, croton butene, fluorenyl, ketone, genomic, triethyl, triisopropyl sulfonyl, phenyl, triphenyl Examples thereof include a base, a triethylidene, a triisopropylidene group, an alkyl group, a tri-example, an oxycarbonyl group, and the like, and examples thereof include a mercapto group, a trisole, a decyl fluorenyl fluorenyl group, and an oil. Sulfhydryl, decyl thiol, cinnabarinyl nicotine ruthenium 5, invention description (57) on decyl, decyldidecyldiisopropyl, fluorenyldiyl, fluorenyl dialkyl, fluorenyl Di-diyldiisopropyl, fluorenyldialkyl, methyl, alkoxypropoxycarbonyl, fluorenyl, hexyl, myristyl, fluorenyl, fluorenyl Sulfhydryl, indole, isodecyl, atol, nicotine, etc. About tricyclodecane fluorene base, iso-stone kiln, third third 矽 矽 夕 院 • • 等 等 等 等 等 等 等 等 等 等 等 等 等 等 等 等 等 等 等 等 等 等Examples of the benzofluorene group include anthraceneoxycarbonyl and the like. Ethyl thiol, propyl sulfonyl aryl, stearin, hexamethylene, propylene, butyl phthalate, naphthyl, acenaphthyl, p-toluene Ethyldipropyl^-methyl;^7 tributyl fluorenyl, stilbene, butyl sulfonium, isoamyl sulfhydryl, oxalate, pepper broth, propyl thiol Examples of the benzhydryl group, the indoylhydrazine group, the benzyl group, the 2-infrathenyl group, and the sulfonic acid cleavable group are exemplified by a cyclopropyl group, a cyclopentamethylene group, and a decane group. A decane-based group, an anthracenyl dithiol group, an ethyldipropyldiindenyltributyldimethylene group, a phenyl group or the like. Base, ethoxy group, hetero group, heptane, laurel, propylene, sebum, methyl dimethyl dithene, hydrogen atropine, hydrazine, etc.

C:\2D-mDE\91-09\91114303.ptd Page 62 13〇4〇6〇5, invention description (58) base, cyclohexyl, 4-tert-butylcyclo, n-decyl, hetero-cyan , tricyclooctane, 4 to methoxycyclohexyl, cyclohexenyl, tetrahydrofuran &tetrahydrothiophene; ^, adamantyl, tetrahydropyranopyrinoyl, 4-helium tetrahydroper Amoxime: tetrahydrothiopyranyl, 3-bromotetrahydrothiophene; [, 1 - dioxin, 4 methoxytetrahydrothiopyranyl, 3 yl, decyl tricyclodecyl, Ethyl±^, 甲八 Fund, alkanoyl, ethyladamantanylpentyl, indolylcyclohexyl, ethyl^^yl, methylcyclopentyl, and ethylcyclo, respectively, represent four carbon atoms a thiol group and at least one of a group of 4 to 20 groups Rig or a group of 4 to 20 groups Rig. , the restriction condition is a monovalent alicyclic hydrocarbon group, or a group R1G, the substituted or unsubstituted bond of the atom, the original uncle, the combination of any two, and the inhibition of the two groups R1G: fire' j> Formed with 4-20 carbon atoms replaced or not taken Bayi fat The hydrocarbonaceous earth, and the remaining R1G is a linear or ^ alkylene group having 4 carbon atoms or a substituted or unsubstituted monovalent fat having 4 to 20 carbon atoms. ^ In these acid cleavable groups, fluorenyl, tert-butoxycarbonyl sulfhydryl, diterpene ethyl, ethoxyethyl, hexaoxyethyl, ethoxypropyl, I group, hydrazine, 1,4-mercaptopropyl, tridecyl, tert-butoxycarbonyl, red t-butyl fluorenyl, heterocyclic, tricyclodecyl, tetrahydropyranyl, tetrahydrofuranyl , tetrahydrothiopyranyl, tetrahydrothiofuranyl, fluorenyl, adamantyl, decyltricyclodecyl, ethyltricyclodecyl, a cyclopentyl, ethylcyclodecyl Further, a fluorenylcyclohexyl group, an ethylcyclohexyl group, a soil-c(p)3 group or the like is preferred. For a clear example of the -C(R1G)3 group, it can be mentioned that (2-positive lattice)_b page 63 C:\2D-CODE\91-09\91114303.ptd 1304060 V. Description of invention (59) Tetrakiladyl 1-(5-hydroxy-2-n-and-one)-[[曱-ylethyl, 2/hexyl-1methylethyl, 1-mono(8-hydroxy-3-tetradecyl) )--曱基乙ί/i甲甲-基)+methylethyl, Bu (3 一基基-Bu Jingang Guangyuan soil I soil ethyl, 2 fluorenyl- 2-n-decyl, 2-mercapto -5-Hydroxy-2-hydroxy-2-adamantyl, etc., 3-methyl~3~tetracyclodecyl, 3-indolyl-8-hydroxy-3_tetracyclodecyl, 2-indole Alkyl-adamantyl, 2-indenyl- 7-, etc. 0, the amount of the acid cleavable group in the resin which is introduced into the cleavable group, the content of each of the cleavable groups of the resin The total number of oxygen functional groups and acid cleavable groups. The number of acid cleavable groups in the) is preferably from 10 to 00%, and more preferably 1 5 1 ΟΟ / g. The type of base soluble resin which is introduced by the cleavage group and the acid cleavable group varies. The polystyrene reduction weight average molecular weight (hereinafter referred to as "Mw") of the resin (A) having an acid cleavable group as measured by gas chromatography is 100,0 0 - 0 0 0, 〇 〇〇 better, ^ 〇〇〇 - 3 〇〇, 〇〇〇 better, and 3, 〇〇〇 1 0 0 0, 0 0 0 is particularly good. The ratio of Mw to the number average molecular weight of polystyrene reduction (hereinafter referred to as "Mn") (Mw/Mn) measured by gel permeation chromatography of a resin containing an acid cleavable group is usually 〇1〇, And I think it is better. These acid-cleavable group-containing resins may be used singly or in combination of two or more. A suitable acid-cleavable group-containing resin using the positive-type radiation-sensitive resin composition (1) of the KrF excimer laser, comprising one or more repeating units of the following chemical formula (10) and one or more Weight of acid cleavable group

C:\2D-OODE\9l -09\91 Π4303 .ptd Page 64 1304060 V. INSTRUCTIONS (60) It is preferred that the compound is insoluble or almost insoluble in alkali resin (hereinafter referred to as "resin ( B 1 )"). The resin (B1) is also suitably used in the positive type radiation-sensitive resin composition (i) using an ArF excimer laser, an F2 excimer laser, an electron beam or the like.

(R11)f(〇H)e wherein R11 represents a hydrogen atom or a monovalent organic group, and e and f are integers from the group 3, which satisfy the formula (e + f) S5. Examples of the repeating unit of the chemical formula (10) can be exemplified by pyrolysis such as 4-hydroxystyrene, 3-hydroxystyrene, 2-hydroxystyrene, 4-hydroxy-α-mercaptostyrene, 3- Mercapto-4-hydroxystyrene, 2-methyl-4-hydroxystyrene, 2-methyl-3-hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxyl A unit derived from a polymerizable unsaturated bond of a compound of styrene, 3,4-dihydroxy-p-ethylene, and 2,4,6-trihydroxystyrene. Among these repeating units, it is obtained by cracking a polymerizable unsaturated bond of 4-hydroxystyrene, 3-hydroxystyrene, 2-styrene, or 4-thio-α-mercaptostyrene. The unit is preferred. With respect to the repeating unit having the acid cleavable group described above, a repeating unit having one or more types of acid functional groups such as a phenolic hydroxyl group and a carboxyl group, a repeating unit represented by the chemical formula (10) or via cleavage (曱) may be mentioned. Acrylic

C:\2D-C0DE\91-09\91114303.ptd Page 65 1304060 V. INSTRUCTIONS (61) Polymerizable unsaturated bonds (the hydrogen atom of the sulfhydryl group or the thiol group is replaced by the aforementioned acid cleavable group) The resulting repeating unit is preferred. A particularly preferred group is a repeating unit obtained by cleavage of a polymerizable unsaturated bond of the following compounds: 4-tert-butoxystyrene, 4-tert-butoxycarbonyloxystyrene, 4-tert-butoxycarbonylhydrazine Oxystyrene, 4-tetrahydropyrene, 4-tetrahydrobenzastyrene, 2-ethoxyethoxystyrene, 2-cyclopentyloxyethoxystyrene, 2-cyclohexyloxy Oxystyrene, tert-butyl (meth) acrylate, methyl adamantyl (mercapto) acrylate, ethyl adamantyl (meth) acrylate, methyl cyclopentyl (meth) acrylate, Ethylcyclopentyl acrylate, nonylcyclohexyl (meth) acrylate, ethylcyclohexyl (decyl) acrylate, and the like. The resin (B 1 ) may include one or more repeating units (hereinafter referred to as "other repeating units (bl)") other than the above repeating unit. As examples of the other repeating unit (b 1), a unit obtained by cracking a polymerizable unsaturated bond of the following compound: a vinyl aromatic compound such as styrene such as styrene, α-mercaptostyrene, or the like may be mentioned. 2-mercaptostyrene, 3-mercaptostyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-nonoxystyrene, and 4-(2 - third (butoxycarbonyl ethoxy) styrene; (fluorenyl) acrylate such as decyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, (fluorenyl) isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl (meth) acrylate, phenyl (meth) acrylate, phenyl ethyl (meth) acrylate, and the following formula (11) - (13) body;

C:\2D-C0DE\91-09\91114303.ptd Page 66 1304060 V. Description of invention (62) 〇ch3 ch3 H2〇=HC—C- 0~ C—( CH2^—C-〇-C—CH =CH2 (11) ch3 g ch3 〇

H2C=HC-E-〇-fcH2

Ο CH2)~〇-C—CH=CH2 (13) where g is an integer of 6; unsaturated carboxylic acids such as (mercapto)acrylic acid, crotonic acid, maleic acid, fumaric acid, and cassia a carboxylic acid; a carboxyalkyl ester of an unsaturated carboxylic acid such as 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, and 3-carboxypropyl (meth)acrylate; unsaturated nitrile group Compounds such as (fluorenyl) acrylonitrile, α-chloroacrylonitrile, crotononitrile, maleic nitrile, and fumaronitrile; unsaturated guanamine compounds such as (fluorenyl) acrylamide, hydrazine, hydrazine Methyl (mercapto) acrylamide, crotonamide, maleimide, and fumaride; unsaturated quinone imine compounds such as maleimide, fluorene-phenyl cis Equinone imine, and fluorene-cyclohexylmethyleneimine;

C: \2D-mDE\91 -09\91114303. ptd Page 67 1304060 V. Inventive Note (63) and other nitrogen-containing B; fcfjj-based compounds, such as N-vinyl-ε-caprolactam, Ν- Vinylpyrrolidone, 2-vinylpyridine, 3-vinylcridine, 4- to ethylene-based bite, 2-acetylimidazole, and 4-vinylimidazole. In these other repeating units (b丨), it is possible to obtain a polymerizable unsaturated bond in a cleavage compound such as α-mercaptostyrene or 4-(2~3 butyloxycarbonylethyloxy)styrene. The unit, the monomer of the formula (丨丨), or the monomer of the formula (12) is preferred. Χ Regarding the acid-containing cleavable group-containing resin of the positive-type radiation-sensitive resin composition (i) using the KrF excimer laser, the phenolic hydroxyl group of the styrene-based epoxy resin may be suitably used. A resin in which an atom is replaced by an acid cleavable group. As examples of preferred acid cleavable groups of the resin, there may be mentioned an ethoxyethyl group, a tert-butyl group, a third butoxycarbonyl group, a third butoxycarbonylmethyl group and the like. A suitable acid-cleavable group-containing resin using the positive radiation-sensitive resin composition (i) of the ArF excimer laser, comprising the following chemical formula (14): or a plurality of repeating units and/or the following chemical formula ( 15) It is preferred that the one or more repeating units are insoluble or hardly soluble in alkali (this resin is referred to as "resin (B2)"). The resin (B2) is also suitably used in the positive radiation type inductive resin composition (i) of KrF excimer laser, ArF excimer laser, & excimer laser, thunder, and the like. Electroacupuncture

C:\2D-CODE\9卜09\91114303.ptd Page 68 '-HO One-CH-A- 1304060

5. Description of the invention (64) wherein B represents a hydrogen atom or an acid cleavable group, at least one b is an acid cleavable group, and D represents a hydrogen atom or a linear or branched chain unit having 1-4 carbon atoms, respectively. Alkyl, and X is an integer from 〇 to 2.

(15)

It is substituted by an atomic unity hydrocarbyl group. For example, R12 represents a hydrogen atom, a methyl group, a burnt group or an all-I group, and R1. a linear or branched alkyl group having 1 to 4 carbon atoms or a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 4 to 2 carbon atoms, or any two ri❹ groups formed to have 4 to 20 carbon atoms a substituted or unsubstituted divalent alicyclic ring, and the remaining R1G group is a substituted or untwisted linear or branched alkyl group having 4 carbon atoms or a taken or 2?

A monovalent alicyclic hydrocarbon group. The preferred repeating unit of the formula (14) is a deuterated frame-tert-butoxycarbonyl bicyclo ring obtained by splitting the polymerizable unsaturated bond of the monomer below [2.2.1] Geng-2-ene

C:\2D-C0DE\91-09\91114303.ptd 1304060 V. Description of the invention (65) 5-(4-Tert-butylcyclohexyloxy)carbonylbicyclo[2·2·1]hept-2-ene, 5-(1-ethoxyethoxy)carbonylbicyclo[2.2.1]hept-2-ene, 5-(1-cyclohexyloxyethoxy)carbonylbicyclo[2·2.1]hept-2-ene, 5 - a third butoxycarbonyl oxime oxycarbonylbicyclo[2.2.1]hept-2-ene, 5-tetrahydrofuranoxycarbonylbicyclo[2·2·1]hept-2-ene, 5-tetrahydropyranyloxycarbonyl Bicyclo[2·2·1]hept-2-ene, 8-t-butoxycarbonyltetracyclo[4·4.0·I2,5·17'1G]dodecane-3-ene, 8-(4) -T-butylcyclohexyloxy)carbonyltetracyclo[4·4·0· I2'5·17'1G]dodecane-3-ene, 8-(1-ethoxyethoxy)carbonyltetracyclo[4 · 4· 0· I2'5· I7,1. ]Dodecane-3-ene, 8-(1-cyclohexyloxyethoxy)carbonyltetracyclo[4·4·0· I2,5·17'1Q]dodecane-3-dilute, 8-third Butoxycarbonylmethoxycarbonyltetracyclo[4·4·0· I2'5·17'1G]dodecane-3-dilute, 8-tetrahydrofuranoxycarbonyltetracyclo[4·4·0· I2'5· 17 '1G] dodecane-3-ene, and 8-tetrahydropyranyloxycarbonyltetracyclo [4. 4. 0·I2'5· 17, 1G ] dodecane-3-ene. Examples of preferred repeating units of the chemical formula (15) include, by means of cleaving (meth)acrylic acid tert-butyl ester, (mercapto)acrylic acid 2-mercapto-2-gold singly, ) 2-ethyl-2-carboacetic acid acrylate, 2-mercaptocyclopentanyl (mercapto) acrylate, 2-ethylcyclopentanyl (meth) acrylate, 2-(fluorenyl) acrylate a unit derived from a polymerizable unsaturated bond of nonylcyclohexyl ester or 2-ethylcyclohexyl (meth) acrylate, and a unit of the following chemical formula (15-1)-(15-12)

C:\2D-CODE\91-09\91114303.ptd Page 70 1304060 V. Description of invention (66) .12

R 12 -(-(p-ch2+· -f - cp-ch2+ 〇=c I 〇 〇=c I o h3oc-ch3 H3C-0 a CH3

OH

(15-3) (15-1) (15-2) • 12

R 12 >12 c-ch2-

〇=c I

〇 I

CH2")~ +9—CH: 〇二9 〇 h3c - έ-ch3Af o=c I 〇

(15-5) (15-6) Round Hill C:\2D-CODE\91-09\91114303.ptd Page 71 1304060 V. Description of Invention (67)

R C 12 o=c I 〇 ch3

HO •ch2+

C — CH2" ch3 R12 Bu c—ch2+ o=c I 〇

(15-7) (15-8)

2 H c 3 H

HO (15-10) (15-11) (15-12) The resin (B 2 ) may include one or more repeating units other than the above repeating unit (hereinafter referred to as "other repeating unit (b2)"). With regard to the other repeating unit (b 2 ), a unit obtained by cracking a polymerizable unsaturated bond of the following compound may be mentioned: a monomer having a nortenylene structure such as deuterated alkene (bicyclo[2·2·1) ]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2·2·1]hept-2-ene, 5-hydroxybicyclo[2] · 2· 1 ]hept-2-ene, 5-fluorobicyclo[2. 2·1 ]hept-2-ene, tetracyclo[4·4·0·I2,5·17,1G]dodecane-3 - alkene, 8-mercaptotetracyclo[4·4. 0· I2,5·17']〇]dodecane-3-ene,

C:\2D-CODE\91-09\91114303.ptd Page 72 1304060

8-ethyltetracyclo[4. 4. 0. I2' iu]dodecane_3_dilute, 8-peryltetracycline [4.4.0.12, 5.17,11)]dodecane_3_ene, 8 - gas tetracyclic [4.4.0.12, 5.17, 1 «)] dodecane-3-ene; unsaturated carboxylic anhydride such as maleic anhydride and itaconic anhydride;

a base acrylate which has been exemplified by other repeating units (bl) of the resin (B1); T (mercapto) propionate 3 - thiol- 1 ~• Acrylate: r13 The following chemical formula (1 6 ) is shown

(16) wherein R represents a gas atom or a sulfhydryl group; When the resin (B2) has the above chemical formula (1, the repeating unit of chuan: butyl succinate is used as the other repeating unit (10) 2. The appropriate formula for the positive-type light-sensitive resin (1) using the F2 excimer laser The resin containing an acid-cleavable group may be an insoluble or almost insoluble alkali-containing polymer comprising the following chemical formula (17): or a plurality of structural units and/or the following chemical formula (18) or a plurality of structural units; Hexane (hereinafter referred to as "resin (B3)"). Resin (B3) contains chemical formula (17)

Page 73 C:\2D-CODE\9 Bu 09\91114303.ptd 1304060 V. The structural unit of the invention (69) is preferred. The resin (B3) is also suitably used in the positive radiation-sensitive resin composition (i) using a KrF excimer laser, an ArF excimer laser, an electron beam or the like. Ε—S—ο— 0

E——S——R ο (17) (18) wherein E represents a monovalent organic group containing an acid cleavable group, and rh is a hydrazine; 1 single: a substituted or unsubstituted direct bond of a Γί atom Preferred examples of the branching bond and the group Ε in (18) include an alicyclic hydrocarbon group of an octadecyl cleavage group (such as a cycloalkyl group, a < fluorenyl group, a tetracyclic fluorenyl group, And adamantane base), can be two: agglomerated aromatic hydrocarbon group and the like. 』 解 解 之 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 - - - - - - - - - - - - Structural unit 17-4).

c(ch3>3 cf3 〇

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C:\2D-CODE\91-09\91114303.ptd Page 75 1304060 V. INSTRUCTION DESCRIPTION (71) The resin (B3) may include one or more structural units other than the aforementioned structural unit (hereinafter referred to as "other structure" Unit (b3)"). With regard to the preferred other structural unit (b3), an alkyl alkoxysilane such as decyltrimethoxy decane, methyltriethoxy decane, ethyltrioxane, ethyltriethoxy decane, etc. may be mentioned. a structural unit obtained by hydrolysis and condensation; and a structural unit represented by the following chemical formulas (18-1) to (18-4). 〇

Cf3 〇

Cf3 (18-2) (18-1)

〇 〇

(18-3) (18-4)

C:\2D-CODE\91-09\91114303.ptd Page 76 1304060 V. INSTRUCTIONS (72) Resin (B 3 ) can be passed through a cleavable group (co) acid cleavable group g polyoxane And the monovalent (co)polycondensation is carried out by continuing the reaction in the acid catalysis to make the Shixi acid-catalyzed acid, nitric acid, acid acid such as citric acid, acid, succinic acid, cis-paraic acid, acetic acid toward: Among them, benzoic acid and vermiculite are particularly preferred for acid amic acid and maleic anhydride. It is obtained by a unit price which will have a polycondensation. In the organic group, an example of an alkane compound in the presence of a reagent, phosphoric acid, acetic acid, maleic acid, or maleic acid. a diacid, an anti-single <bean organic group of a decane compound and an acid or by introducing an acid cleavable group and/or an organic group to the previously prepared organic compound, and a chemical; It is preferred to carry out polycondensation of malonic acid, p-formic acid, an enedioxane compound and an acid cleavable group acidic catalyst as a catalyst, and it is particularly preferable to add an alkali catalyzed reaction. , y cite inorganic acids such as hydrogen tetrachloride titanium chloride, chlorination and aluminum chloride propionic acid, butyric acid, valeric acid, oxalic acid, fumaric acid, adipic acid, sebacic acid anhydride, citric acid Examples of the catalysts of benzenesulfonic acid, chlorous acid, sulfuric acid, acetic acid, squalic acid, acetic anhydride, and cis-butylate include inorganic bases such as lithium, sodium telluride, and potassium hydroxide. Calcium hydroxide, barium hydroxide, hydrazine, sodium, acid hydrogen, sodium carbonate, and potassium carbonate; organic tests such as = a hydrogen tri-n-propylamine, tri-n-butylamine, and hydrazine. _ Bfee, test soluble tree month j solution tree can be used in the positive type radiation sensitive resin composition (i i), the resin has one or more exhibiting affinity with the alkaline developing solution =

C:\2D-OODE\91-O9\91114303.ptd Page 77 1304060 V. Description of the invention (73) Base, for example, a resin containing an oxygen S-sulfenyl group such as a phenolic hydroxyl group, an alcoholic hydroxyl group, or a carboxyl group. Examples of the retortable resin include an addition polymerization resin having one or more repeating units of the following chemical formulas (1 9 ) to (2 1), and having one or more repeats of the following chemical formula (2 2 ) A polycondensation resin of the unit.

2^~ o=c

OH

o=cc=〇II OH OH (20) (21) wherein R15 and R17 represent a hydrogen atom or a fluorenyl group, respectively, Rie represents a hydroxyl group, a carboxyl group, -R18C00H, -ORRC00H, -0C0R18C00H, or -COOR18COOH (R18 represents a group respectively) -(C H2 )h -, where h is an integer from 1 to 4).

Wherein R19 represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, respectively. In the case of an alkali-soluble resin-based addition polymerization resin, the resin may be

C:\2D-CODE\91-09\911143O3.ptd Page 78 1304060 V. INSTRUCTIONS (74) Formed only by repeating units of formula (19) to (21), or may further comprise one or more other repeats The unit (hereinafter referred to as r other repeating unit (c丨)) may be used as long as the resin is soluble in the alkaline developer. Examples of the other repeating unit (c 1 ) include other repeating units (b 1) of the resin (β丨) and the like. In the case of the test of the glutamic resin-based polycondensation resin, the resin may be formed only by the repeating unit of the formula (22), or may further comprise one or more other repeating units (hereinafter referred to as "other repeating units ( 〇 2)"), as long as the fat can be dissolved in the alkaline developer. Although it is generally impossible to specify the weight of the chemical formula (1 9 ) to (2 2 ) in the alkali-soluble resin, the content of the unit, and it varies depending on the type of other repeating unit (cl) or other repeating unit (c2), but The content is preferably 1 〇 -1 〇〇 Molar percentage, and 2 0 - 1 0 0 mole percentage is better. Knife When the resin has a repeating unit containing a carbon-carbon unsaturated bond, such as, for example, a repeating unit of the formulae (19) and (22), the alkali-soluble resin can be used as a hydride. In this case, the degree of hydrogenation is usually 70% or less of the total amount of the repeating unit of the formula (1 (2 2 ), and other similar repeating units, >6 counter; 5 anti-Russian mouth bonds, at 50% or Preferably, β 4 U % or less is more preferable. If the degree of hydrogenation is more than 70%, the developability of the base can be reduced by using the alkali dye. §Injection-sensitive resin composition (ii) 1 <alkali can be used: nucleus and fat, including poly(4-hydroxystyrene), 4-hydroxyl stupid /" for ten 匕 cloth / 4-hydroxy one Methyl styrene copolymer, 4-Phenylstyrene/Stupid ethylene copolymerization «- The resin of the main component is especially good.

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Page 81 1304060

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P.82, 1304060, wherein R2G represents an acid cleavable group or a third butoxycarbonyl group, respectively, and ρ represents a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, or a naphthyl group, respectively. a linear or branched alkyl group representing a hydrogen atom, having 4 carbon atoms, or a phenyl group, Q representing a single bond, -0-, -S-, -c〇-, -c〇〇-, -SO -, -S02-, -C(R23)(R24)—(wherein R23 and 妒 respectively represent a hydrogen atom, a straight or branched alkyl group having 6 carbon atoms, and a linear chain having 2 to n carbon atoms Or a branched chain, a phenyl group, or a fluorenyl-naphthyl group, or a substituted or unsubstituted phenyl group, p, q, r, s, t, u, v, and w represent an integer of 〇 or more 'The limiting condition is 5 - p - 1 of the chemical formula (2 3 ), lOMp + r)-;!, the chemical formula (25) 215-(p + r + t)-i, the chemical formula (26) 20-(p + r + t + v)-i, and 19^(p + r + t + v) - 1 of the formula (27); steroids (bile acids) such as cholic acid, deoxycholic acid, and A cholesteric acid compound containing an alicyclic ring or an aromatic ring such as adamantane carbonic acid or diamond The hydrogen atom of the carboxyl group in the carbonic acid compound is substituted by the aforementioned acid cleavable group or the third butoxycarbonylmethyl group; and the like. As the high molecular weight solubility control agent, for example, the aforementioned acid cleavable group-containing resin can be used. Preferred alkali solubility control agents for the positive-type light-sensitive resin composition include steroids (bile acids) such as cholic acid, deoxycholic acid, and stone biliary I 'lipid-containing ring Or a compound of an aromatic ring such as adamantane carbonic acid or a ruthenium carboxylic acid wherein a hydrogen atom of a carboxyl group in the carbonic acid compound is substituted with the aforementioned acid cleavable group or a third butoxycarbonyl group. These solubility control agents may be used singly or in combination of two or more.

1304060 V. INSTRUCTION OF THE INVENTION (79) J-type radiation-sensitive resin composition The negative-type radiation-sensitive resin composition of the present invention (hereinafter referred to as "negative radiation-sensitive resin composition (iii)") includes ··( A) acid generator (I), (C) test > trough resin ' and (E) cross-linking in the presence of acid to dissolve the compound of the tree sorghum (hereinafter referred to as "crosslinking agent (E) "). As the acid generator (I) used in the negative-type radiation-sensitive resin composition (i i i ), an acid generator having thermal and chemical stability is preferred. The negative-type radiation-sensitive resin composition (i i 丨) of the present invention will now be explained. In the case of the alkali-soluble resin of the negative-type radiation-sensitive resin composition (i i i ), a resin exemplified as the positive-type radiation-sensitive resin composition (i丨) can be cited. A resin which is soluble in a negative-type photosensitive resin composition (iii), comprising poly(4-hydroxystyrene), 4-hydroxystyrene/4-hydroxy-α-mercapto-styrene copolymer, A resin having a 4-hydroxystyrene/styrene copolymer or the like as a main component is preferred. Although the Mw of the alkali-soluble resin varies depending on the desired characteristics of the negative-type radiation-sensitive resin composition (111), the preferred range is 丨, 〇〇〇-15〇, 〇〇〇' at 3,000- 100, the range of 〇〇〇 is better. These alkali-soluble resins may be exemplified by the crosslinking agent (8), or the crosslinking agent (E), or the crosslinking agent (E), which has one or more of the crosslinking agent (8). A compound which exhibits cross-linking reactivity with an alkali-soluble resin (hereinafter referred to as "crosslinkable functional group").

C:\2D-CBDE\91-09\91114303.ptd Page 84 1304060 V. INSTRUCTIONS (80) Examples of the coupleable g-energy group include glycidyl ether group and shrinkage oil vinegar base: shrinkage Glycerylamino, oxime methyl, ethoxymethyl, octylmethoxy, ethoxymethyl, benzylideneoxymethyl, decyl, ethylidene, vinyl, isopropenyl, (di) Amino) fluorenyl, (diethylamino)methyl, (di-methylfef) methyl, (dihydroxyethylamino) fluorenyl, florin fluorenyl, and the like. _About the parental agent (E), bisphenol a epoxy compound, bisphenol F epoxy compound, bisphenol s epoxy compound, novolac epoxy resin epoxy compound, and phenol novolac epoxy resin a compound, a poly(hydroxystyrene) epoxy compound, a hydroxymethyl group-containing melamine compound, a methylol group-containing benzoguanamine compound, a hydroxymethyl group-containing compound, a hydroxy group-containing phenol compound, and a Alkoxyalkyl melamine compound, alkoxyalkyl group-containing benzoguanamine compound, alkoxyalkyl group-containing urea compound, alkoxyalkyl group-containing phenol compound, carboxy group-containing melamine resin, carboxymethyl group-containing Benzoylamine resin, carboxymethyl group-containing urea resin, carboxymethyl group-containing phenol resin, carboxy group-containing melamine compound, carboxymethyl group-containing benzoguanamine compound, carboxymethyl group-containing urea compound, carboxy group containing carboxy group Base phenolic compounds and the like. Among these crosslinking agents (E), a compound containing a methyl group, a melamine compound containing a methoxymethyl group, a phenol compound containing an anthracene group, an acetylene urea compound containing a decyloxymethyl group, and the like The oxonium-based urea compound and the acetoxymethyl-containing phenol compound are preferably 'excellent compounds are methoxymethyl-containing melamine compounds such as hexamethoxymethyl melamine) and methoxy-containing groups. A group of urea urea compounds, a compound containing a methoxymethyl group, and the like. The methoxyl-containing melamine compound can be found in the market under the registered trademarks cymel3〇〇, CYMEL3 (H, CYMEL3〇3, and CYMEL3G5 (MUsui c-d)

Page 85 1304060 V. INSTRUCTIONS (81) Manufactured by C〇·, Ltd., an oxyacetylene-containing acetylene urea compound is commercially available from Mitsui Cyanamid Co., Ltd. under the 5-booklet trademark CYMEL 1174. And the like; and the hydrazine-containing urea compound is commercially available under the registered trademark MX2 90 (manufactured by Sanwa Chemical Co., Ltd.) and the like. A resin having a crosslinking agent property by substituting a hydrogen atom of an oxygen-containing functional group in the alkali-soluble resin with the aforementioned crosslinkable functional group may be suitably used as the crosslinking agent (E). Although a clear percentage may vary depending on the type of alkali-soluble resin that can be introduced by the crosslinkable functional group and the crosslinkable functional group, the amount of the pg energy base that can be introduced is usually the total oxygen-containing function in the soluble resin. The 5-60 mole percentage of the base is preferably from 1 to 50 mole percent, and more preferably from 1 to 5 to 40 mole percent. An amount of crosslinkable functional group of less than 5 moles reduces the residual coating rate and tends to cause distortion and expansion of the pattern. If the amount exceeds 60% by mole, the visibility of the exposed area tends to decrease. A crosslinking agent (g) which is a negative light-sensitive resin composition (i i i ) is preferably used as a negative light-sensitive resin composition (i i i ) containing a ruthenium sulfonium-containing compound such as dioxonium carbazide and a ruthenium oxyfluoride. The crosslinking agent (E) may be used singly or in combination of two or more. Other acid-removing wah-positive type radiation-sensitive resin composition (i), positive-type radiation-sensitive resin composition (ii), and negative-type radiation-sensitive resin composition (iii) may contain an acid-removing agent as needed ( I) An acid generator (hereinafter referred to as "other acid generator"). Examples of other acid generators include sulfonimide compounds and moths.

C:\2D-CODE\91-O9\91114303.ptd Page 86 1304060 V. INSTRUCTIONS (82) Salt compounds, antimony compounds, acid-retaining compounds, diterpenoid diazonium terbene compounds, disulfonate A methane compound, a sulfonium sulfonate compound, a sulfonium sulfonate compound or the like Examples of such other acid generators are as follows: <Cityrite-imine compound> Examples of the sulfonimide compound include compounds of the following chemical formula (2 8 ): α

II people 〇

^ \ II

^Ν-0-S-R25 (28) C 〇

II 0 wherein R 25 is a monovalent organic group, and R 26 is a divalent organic group. Clear examples of the retinoid compound include N-(trifluorosulfonium oxysulfonate) amber quinone imine, N-(three-defected scutellite), yttrium imine, N-(trifluorosulfonate) Oxygen) diphenyl maleimide,

N-(Trifluorosulfonium sulfonium oxy)bicyclo[2. 2.1]hept-5-ene-2,3-dicarboxyarsenine, N-(trifluorosulfonium oxy)-7-vf bicyclo [2. 2. 1 ]hept-5-ene-2,3-dicarboxyarsenine, N-(trifluorosulfonium oxy)bicyclo[2·2·1]hept-5,6-oxo-2, 3 - Dicarboxylated imine,

C:\2D-CODE\91-09\91114303.ptd Page 87 1304060 V. INSTRUCTIONS (83) N-(Trifluoromethanesulfonyloxy)naphthoquinone imine, N - ( 1 0 - off-brain Oxygen) ό ό 亚 亚 亚 亚 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( (1 0 - camphor sulfonium oxy) bicyclo [2· 2· 1 ]hept-5-ene-2,3-dicarboxyarmine imine, Ν-(10-offbrain acid oxygen)-7-, double ring [2·2·1]hept-5-rare-2,3-dipropionimine, Ν-(10-camphorsulfonyloxy)bicyclo[2. 2·1 ]hept-5,6-oxo-2, 3 - Dicarboxy quinone imine: ό 氧 氧 ) ) ) ) ) ) ) ) ) ) ) ) ) 10 10 10 10 10 10 10 10 正 正 正 正 正 正 正 正 正 正 正 正 正 2 2 2 2 2 2 2 2 [f 醯 环 Ϊ Ϊ 酞 酞 双 bis -7 λ y λ y y y y y y y y y y y y y y y y y y y y y y y y y 1 Alkenylene poor dish _ ^. -) _- amine sub-S S slow %3 / yttrium carboxy ring dioxin sulfonate n-heptyloxy hydrazine carboxamide, imine 醯 醯 醯 萘 naphthalene I) } Oxygen Sulphur sulfonate February knife. Yaki [2 醯 酞 酞 酞 双 ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) 4 4 4 4 4 4 4 4 4月j 亚烯^皿_ @13 亚carboxy C:\2D-CODH\91-09\91114303.ptd Page 88 1304060 V. Description of invention (84) Amine, N-(p-toluenesulfonyloxy)-7 - ·ρ|bicyclo[2·2·1]hept-5-ene-2,3-dicarboxyarsenine, N-(p-phenylenesulfonyloxy)bicyclo[2.2.1]hept-5, 6 - Oxygen-2,3-dicarboxylimine, N-(p-toluenesulfonyloxy)naphthylimine, N-(2-trifluorotoluenesulfonyloxy)arene, N-(2-three Fluoroquinone sulfonium oxy) quinone imine, N - ( 2 -trifluorobenzene sulfonium oxy) diphenyl maleimide, N-(2-three gas toluene yellow oxygen) double ring [2.2.1] G-5 - dilute-2,3 - diweilanimine, N-(2-trifluorosulfonylsulfonyloxy)-7-pfbicyclo[2·2.1]hept-5- Aceene-2,3-dicarboxylimine imine, N-(2-trifluorotoluenesulfonyloxy)bicyclo[2.2.1]hept-5,6-oxo-2,3-dicarboxyarmine, N-(2-trifluorobenzenesulfonyloxy)naphthylimine, N-(4-trifluorosulfonium oxysulfonate) amber quinone imine, N- ( 4-trifluorobenzenesulfonyloxy) quinone imine, N-(4-trifluorotoluenesulfonyloxy)diphenylbutyleneimine, N-(4-trifluorosulfonium sulfonate Bicyclo[2·2·1]hept-5-ene-2,3-dicarboxyindoleimine, N-(4-trifluorosulfonylsulfonyloxy)-7-bicyclo[2·2·1]g -5-ene-2,3-dicarboxyarsenine, N-(4-trifluorotoluenesulfonyloxy)bicyclo[2·2.1]hept-5,6-oxo-2,3-dicarboxylate

C:\2D-CODE\91-09\91114303.ptd Page 89 1304060 V. INSTRUCTIONS (85) Yttrium, N-(4-trifluorosulfonyloxy)naphthylimine, N-( All gas benzene continued S basket oxygen) 虎 Tiger J0 brewed imine, Ν - (perfluorobenzene continued oxygen) quinone imine, Ν - (perfluorobenzene sulfonate) diphenyl maleimide , Ν-(perfluorobenzenesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenine, Ν-(perfluorobenzenesulfonyloxy)-7-qiaobicyclo[2 · 2. 1 ]hept-5-ene-2,3-dicarboximine, N-(perfluorobenzenesulfonyloxy)bicyclo[2.2.1]hept-5,6-oxo-2, 3 -di Carboxylium imine, N-(perphenylene hydrazine) naphthyl imide, N-(1-naphthosulfonyloxy) amber quinone imine, N-(1-naphthosulfonyloxy) quinone imine, N - (1-naphthalene sulfonium oxy) diphenyl maleimide, 1^-(1-naphthalenesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium imine, Ν-(1-naphthylxanthineoxy)-7-^bicyclo[2·2·1]hept-5-lean-2,3-di-resolic acid imine, N-(l-naphthalene sulfonate Oxide)bicyclo[2. 2·1 ]hept-5,6-oxo-2,3-dicarboxyarsenine, Ν-(1-naphthalenesulfonyloxy)naphthoquinone imine, Ν-(phenylsulfonate) Oxygen) amber Amine, Ν - (Benzene Sulfonic oxy) phthalocyanine (PEI), Ν - (Benzene Sulfonic oxygen) diphenyl maleic (PEI)

C:\2D-CODE\91-09\91114303.ptd Page 90 1304060 V. INSTRUCTIONS (86) N-(Phenyl Yellow Oxygen) Bicyclo[2·2·1]hept-5-rare_2, 3_II, S-Imine, Ν-(phenylsulfonyloxy)-7-indole bicyclo[2·2·1]hept-5-ene-2,3-dicarboxyarmine, Ν-(benzenesulfonate醯oxy)bicyclo[2·2.1]hept-5,6-oxo-2,3-dicarboxyarminemine, Ν-(phenylsulfonyloxy)naphthylimine, Ν-{ (5-fluorenyl) -5-曱Oxycarbonylbicyclo[2·2.1]hept-2-yl)sulfonyloxy}succinimide, Ν-{(5-methyl-5-methoxycarbonylbicyclo[2·2 · 1 ] Geng- 2 - base) sulphate oxime} bicyclo [2 · 2. 1] hept-5 - dilute-2,3 - diweilanimide and the like. &lt;Nominal salt compound> Examples of the salt compound include an onium salt, a house I salt (including a thiophene salt), a scale salt, a diazo pure salt, a money salt, and a σ ratio bond salt. Clear examples of the salt 1 include: bis(4-tert-butylphenyl)phosphonium trifluorosulfonate, bis(4-tert-butylphenyl)phosphonium sulfonate, and bis-dodecylbenzenesulfonic acid bis (4) -T-butylphenyl)anthracene, bis(4-t-butylphenyl)phosphonium p-toluenesulfonate, bis(4-tert-butylphenyl)phosphonium benzenesulfonate, 10-camphorsulfonic acid bis (4- Tributylphenyl)anthracene, bis(4-tert-butylphenyl)phosphonium n-octylsulfonate, bis(4-t-butylphenyl)phosphonium 2-trifluoromethylbenzenesulfonate, 4-trifluoromethylsulfonyl Bis(4-tert-butylphenyl)phosphonium benzenesulfonate, bis(4-t-butylphenyl)phosphonium perfluorobenzenesulfonate, diphenylphosphonium trifluoride,

C: \2D-mDE\91 -09\91114303 .ptd Page 91 1304060 V. Description of invention (87) Diphenyl sulfonium sulfonate, diphenylene phthalate, diphenyl benzene sulfonate Bismuth, diphenyl sulfonate, 1 0 - camphoric acid diphenyl lock, n-octyl sulfonate diphenyl hydrazine, 2-trifluorodecyl benzene sulfonic acid diphenyl hydrazine, 4 - trifluoromethyl benzene sulfonic acid Benzoquinone, diphenyl sulfonium perfluorobenzenesulfonate, di(p-tolyl) fluorene trifluorosulfonate, bis(p-phenylene) sulfonate, n-dodecyl benzoic acid ), lock, p-toluenesulfonic acid di(p-phenylene) fluorene, bis(p-phenylphenyl) sulfonate, 10 -camphorsulfonic acid bis(p-tolyl) fluorene, n-octane sulfonate Tolyl) ruthenium, di(p-phenylphenyl)phosphonium 2-trifluorodecylbenzenesulfonate, di(p-phenylphenyl)phosphonium 4-trifluorodecylbenzenesulfonate, di-p-perfluorobenzenesulfonate Phenyl) ruthenium, bis(3,4-didecylphenyl)phosphonium trifluoromethanesulfonate, bis(3,4-dimercaptophenyl)phosphonium sulfonate, n-dodecylbenzenesulfonic acid 3,4-dimercaptophenyl)anthracene, p-tert-benzenesulfonate bis(3,4-dimercaptophenyl)anthracene, benzenesulfonic acid bis(3, 4-dimethylphenyl) hydrazine,

C:\2D-CODE\91-09\91114303.ptd Page 92 1304060_ V. INSTRUCTIONS (88) 10-camphorsulfonic acid bis(3,4-dimercaptophenyl)anthracene, n-octanesulfonic acid II 3,4-dimercaptophenyl)anthracene, bis(3,4-didecylphenyl)anthracene, 4-trifluorodecylbenzenesulfonic acid bis(3,4- Dimethylphenyl)-locked, bis(3,4-dimercaptophenyl)fluorene perfluorobenzenesulfonate, 4-nitrophenylphenyl ester of trifluorosulfonium sulfonate, 4-nitrophenyl sulfonate • Phenyl hydrazine, n-dodecyl phenyl sulfonate, 4-nitrophenyl phenyl hydrazine, 4-phenylphenyl phenyl hydrazine, 4-nitrophenyl phenyl benzene sulfonate 1 0 - camphorsulfonic acid 4 - nitrophenyl phenyl lock, n-octyl acid 4 - stone phenyl phenyl fluorene, 2-trifluorodecyl benzene sulfonic acid 4 - nitrophenyl phenyl hydrazine, 4-trifluorodecylbenzenesulfonic acid 4-nitrophenyl phenyl sulfonium, perfluorobenzenesulfonic acid 4-nitrophenyl phenyl hydrazine, trifluorosulfonium sulfonic acid bis(3-nitrophenyl) fluorene, hydrazine Di(3-nitrophenyl)phosphonium sulfonate, bis(3-nitrophenyl)phosphonium n-dodecylbenzenesulfonate, bis(3-nitrophenyl)phosphonium sulfonate, benzoic acid di(3) - indeed phenyl) 錤, 1 〇-樟Cerebral sulfonic acid bis(3-nitrophenyl)anthracene, n-octyl acid bis(3-phenylene) fluorene, 2-trifluoromethylbenzenesulfonic acid bis(3-nitrophenyl)phosphonium, 4-trifluoro Di(3-nitrophenyl)fluorene decylbenzenesulfonate,

C:\2D-mDE\91-09\91114303.ptd Page 93 1304060_ V. INSTRUCTIONS (89) Perfluorobenzenesulfonic acid bis(3-nitrophenyl)-locked, trifluoroanthracene 4-oxobenzene Phenyl hydrazine, hydrazine sulfonate 4-decyloxyphenyl phenyl hydrazine, n-dodecyl benzene sulfonic acid 4-nonyloxyphenyl phenyl fluorene, p-toluene sulfonic acid 4-methoxyphenyl Phenyl hydrazine, 4-methoxyphenyl phenyl sulfonate, 4-methoxyphenyl phenyl hydrazine, 4-methoxyphenyl phenyl hydrazine, 2 4-trimethoxyphenylsulfonic acid 4-methoxyphenyl•phenylhydrazine, 4-trifluorodecylbenzenesulfonic acid 4-nonyloxyphenyl•phenylhydrazine, perfluorobenzenesulfonic acid 4-methoxyphenyl • Phenylhydrazine, bis(4-chlorophenyl) sulfonate, bis(4-chlorophenyl)phosphonium sulfonate, n-dodecyl benzoic acid di(4-phenylphenyl) lock, P-(4-chlorophenyl)phosphonium benzenesulfonate, bis(4-chlorophenyl)phosphonium benzoate, bis(4-chlorophenyl) pin of 10-camphorsulfonate, n-octyl acid (4) - gas phenyl) lock, bis(4-chlorophenyl)phosphonium 2-trifluorodecylbenzenesulfonate, bis(4-phenylphenyl)phosphonium 4-trifluorodecylbenzenesulfonate, perfluorobenzenesulfonic acid Bis(4-phenylphenyl)anthracene, Bis(4-trifluorodecylphenyl) fluoromethionate, bis(4-trifluoromethylphenyl)-locked bis(4-trifluoromethylphenyl) n-dodecylbenzenesulfonate Base)

C:\2D-CODE\91-09\91114303.ptd Page 94 1304060_ V. INSTRUCTIONS (90) P-(4-trifluoromethylphenyl) sulfonium sulfonate and bis(4-phenylene sulfonate) Trifluoromethylphenyl)anthracene, 10-camphorsulfonic acid bis(4-trifluorodecylphenyl)anthracene, n-octylsulfonic acid bis(4-trifluorodecylphenyl)anthracene, 2-trifluorodecyl Bis(4-trifluorodecylphenyl) benzenesulfonate, bis(4-trifluoromethylphenyl) 4-trifluorodecylbenzenesulfonate, di(4-trifluoroindole) perfluorobenzenesulfonate Phenyl) ruthenium, di(1-naphthyl)phosphonium trifluorosulfonate, bis(1-naphthyl)phosphonium triflate, bis(1-naphthyl)phosphonium nonafluorobutanesulfonate, Oxygen n-octanoic acid di(1-naphthyl)-lock, bis(1-naphthyl)anthracene sulfonate, di(1-naphthyl)anthracene n-dodecylbenzenesulfonate, p-toluenesulfonic acid di(1) -naphthyl)anthracene, benzoic acid di(1-methyl)-lock, 10-camphorsulfonic acid di(1-naphthyl)anthracene, n-octylsulfonic acid di(1-naphthyl)anthracene, 2-trifluoroanthracene Di(1-naphthyl)anthracene benzenesulfonate, di(1-naphthyl)anthracene 4-trifluorodecylbenzenesulfonate, di(1-naphthyl)phosphonium perfluorobenzenesulfonate, trifluorosulfonium sulfonic acid Phenylhydrazine Biphenyl-Ji extending pyrene sulfonate, n-dodecyl benzene correct lock acid stretch biphenyl, benzene Yue performance of biphenyl acid stretch lock,

C:\2D-CODE\91-09\91114303.ptd Page 95 1304060 V. INSTRUCTIONS (91) Benzenesulfonic acid extended biphenyl hydrazine, 10 0-camphorsulfonic acid extended biphenyl hydrazine, n-octane sulfonic acid Diphenyl fluorene, 2-trifluorodecylbenzenesulfonic acid, phenylhydrazine, 4-trifluorodecylbenzenesulfonic acid, phenylhydrazine, perfluorobenzenesulfonic acid, phenylhydrazine, trifluoroanthracene Sulfonic acid 2-chloro-terphenyl hydrazine, sulfonic acid 2-chloro-terphenyl fluorene, n-dodecyl benzoic acid 2-chloro-extension phenyl lock, p-toluenesulfonic acid 2-chloro-stranded biphenyl Base, 2-chlorobenzene phenyl sulfonate, 1 0 - camphorsulfonic acid 2 - gas extended biphenyl hydrazine, n-octyl sulfonate 2-chloro phenyl hydrazine, 2-trifluorodecyl benzene Sulfonic acid 2-gas extension biphenyl hydrazine, 4-trifluoromethylbenzenesulfonic acid 2-chloro-terphenyl fluorene, perfluorobenzenesulfonic acid 2_chloro-terphenyl fluorene, tri-II fluorite Benzene such as 'U, sulfonate triphenyl f, n-dodecylbenzenesulfonic acid triphenyl, p-toluene acid diphenyl right", benzenesulfonic acid triphenyl fluorene, 1 0 - camphorsulfonic acid triphenyl, positive Succinic acid triphenyl, 2-trifluorodecylbenzenesulfonic acid triphenyl i tiger,

C:\2D-CODE\91-09\9m4303.ptd Page 96 1304060 V. Description of invention (92) 4-trifluorodecylbenzenesulfonic acid triphenyl, hexafluoroantimonic acid triphenylene, naphthalenesulfonic acid Benzene anti-t, perfluorobenzenesulfonic acid triphenyl hydrazine, trifluorosulfonium sulfonate 4-tert-butylphenyl diphenylate R, sulfonic acid 4-tert-butylphenyl diphenyl f fear, positive ten 4-tert-phenylenesulfonic acid 4-tert-butylphenyl diphenyl fluoride, p-toluenesulfonic acid 4-tert-butylphenyl diphenyl phthalate, 4-phenylbutyric acid • diphenyl sulfonium sulfonate, 10 - camphorsulfonic acid 4-t-butylphenyl diphenyl #1, n-octanesulfonic acid 4_t-butylphenyl diphenyl weeping, 2-trifluorodecylbenzenesulfonic acid 4-tert-butylphenyl • Diphenyl fluorene, 4-trifluorodecylbenzenesulfonic acid 4-tert-butylphenyl diphenyl #☆, perfluorobenzenesulfonic acid 4-tert-butylphenyl diphenyl, trifluoromethanesulfonic acid 4 -T-butoxyphenyl·diphenyl book t, sulfonate 4-tert-butoxyphenyl diphenyl gas, n-dodecylbenzenesulfonate 4-tert-butoxyphenyl diphenyl spar, For the sale of p-toluenesulfonic acid 4-tert-butoxyphenyl diphenyl, benzenesulfonic acid 4-tert-butoxyphenyl diphenyl H, 10-camphorsulfonate 4-t-butoxyphenyl diphenyl Cut ^, n-octanesulfonic acid 4- Tributoxyphenyl diphenyl phthalate, 2-trifluorodecylbenzenesulfonic acid 4-tert-butoxyphenyl dibenzofuran, 4-trifluorodecylbenzenesulfonic acid 4-tert-butoxybenzene Base diphenyl fe, perfluorobenzenesulfonic acid 4-th-butoxyphenyl diphenyl is sold,

C:\2D-CODE\91-09\91114303.ptd Page 97 1304060 V. INSTRUCTIONS (93) 4-Hydroxyphenyl•diphenyl Itine, tribasic acid 4-Phenyl-2-diphenyl隹, n-dodecylbenzenesulfonic acid 4-hydroxyphenyl • diphenyl hydrazine, p-toluenesulfonic acid 4-hydroxyphenyl • diphenyl, benzene sulfonic acid 4-hydroxyphenyl • diphenyl € 1, 10 - camphorsulfonic acid 4-hydroxyphenyl diphenyl sharp, n-octylsulfonic acid 4-hydroxyphenyl diphenyl, 1, 2-trisylbenphate, 4-phenyl-diphenyl; 4-trifluorophenylbenzenesulfonic acid 4-hydroxyphenyl•diphenyl.1.

4-fluorophenyl sulfonate, diphenyl sulfonate, trifluoromethanesulfonic acid ginseng (4 曱 oxyphenyl), sulfonic acid sulfonate (4-oxophenyl phenyl emulsion, n-dodecyl) Benzene sulfonic acid ginseng (4-anthoxyphenyl) ft, p-toluenesulfonic acid ginseng (4-anthoxyphenyl) | moxibustion, benzene sulfonic acid ginseng (4-methoxyphenyl) moxibustion, 1 0 - camphor sulfonate Acid ginseng (4-oxophenyl) 1, octanoic acid sulfonate (4-oxophenyl) &lt;11, 2-tris-fluorononylbenzenesulfonic acid ginseng (4-anthoxyphenyl) ,

4-trifluorodecylbenzenesulfonic acid ginseng (4-anthoxyphenyl) 1, perfluorobenzenesulfonic acid ginseng (4-oxophenyl) &lt;|cry, trifluorosulfonate bis(4-anthracene) Oxyphenyl)·p-phenylene #1, sulfonic acid bis(4-indolylphenyl)·p-toluene f, n-dodecyl benzoate, bis(4-indolylphenyl)·p-toluene , 1, p-toluenesulfonic acid bis(4-indolylphenyl)·p-benzene,

C:\2D-C0DE\91-09\91114303.ptd Page 98 1304060 V. INSTRUCTIONS (94) Di(4-anthoxyphenyl)benzenesulfonate·p-phenylene H, 1 0-camphorsulfonic acid (4-oxophenyl)·p-benzopyrene, n-octylsulfonic acid bis(4-methoxyphenyl)·p-benzoquinone c, 2-trifluoromethylbenzenesulfonic acid bis(4-indolylbenzene ))·p-Benzene 1 rabbit, 4-(4-pyridylphenyl)-p-phenylene perfluorobenzenesulfonic acid bis(4-indolylphenyl)-p-benzoquinone t, trifluorosulfonium sulfonate phenyl • biphenyl ft, hydrazine sulfonate phenyl • extended biphenyl phthalate, n-dodecyl benzene sulfonate phenyl • extended biphenyl sold, p-toluenesulfonic acid Phenyl • phenyl phenyl fluorene, phenyl benzene sulfonate • biphenyl phenyl f R, 1 0 - camphorsulfonyl phenyl • biphenyl phenyl, n-octyl sulfonate phenyl • biphenyl 2-trifluorodecylbenzenesulfonic acid phenyl • biphenyl, 4-trifluorodecylbenzenesulfonate phenyl • biphenyl phenyl t, perfluorobenzene sulfonate phenyl • biphenyl phenyl f , trifluorosulfonium sulfonic acid (4-phenylthiophenyl) diphenyl sulfonium, sulfonic acid (4-phenylthiophenyl) diphenyl f: negative, n-dodecylbenzenesulfonic acid (4-benzene sulfur Phenyl)· Benzene f^, p-benzoic acid (4-phenylthiophenyl)·diphenylhydrazine/U, benzenesulfonic acid (4-phenylthiophenyl)·diphenyl ginseng i, 10-camphorsulfonic acid (4-benzene) Thiophenyl)·diphenyl silver, n-octylsulfonic acid (4-phenylthiophenyl)·diphenyl, 1, 2-trifluorodecylbenzenesulfonic acid (4-phenylthiophenyl)·diphenyl,

C:\2D-OODE\91-O9\91114303.ptd Page 99 1304060 V. INSTRUCTIONS (95) 4-Trifluorodecylbenzenesulfonic acid (4-phenylthiophenyl)·diphenylene t, perfluoro Benzoic acid (4-phenylthiophenyl) diphenyl, bis(trifluoromethanesulfonate) 4,4 '-bis(diphenyldihydrothiophenyl)sulfide, di(anthracenesulfonic acid) 4,4 '-bis(diphenyldihydrothiophenyl)sulfide, bis(n-dodecylbenzenesulfonic acid) 4,4 '-bis(diphenyldihydrothiophenyl)sulfide, bis(p-toluenesulfonic acid) 4,4 '-bis(diphenyldihydrothiophenyl)sulfide, bis(benzenesulfonic acid) 4,4 '-bis(diphenyldihydrothiophenyl)sulfide, bis(10-camphorsulfonic acid) 4, 4'-bis(diphenyldisulfonylthio)sulfide, bis(n-octanoic acid) 4,4'-bis(diphenyldihydrothiophenyl)sulfide, bis(2-trifluoro) Toluenesulfonic acid) 4,4'-bis(diphenyldihydrothiophenyl)sulfide, bis(4-trifluoroindolenesulfonic acid) 4,4 '-bis(diphenyldihydrothiophenyl)sulfide , bis(perfluorobenzenesulfonic acid) 4,4'-bis(diphenyldihydrothiophenyl)sulfide, triphenylsulfonium sulfonate 1-phenyltetrahydrothiophene per t, trifluorosulfonium sulfonic acid l-( 4-hydroxyphenyl Tetrahydrothiophene-, tris(trimethylenesulfonate)-(3,5-dimercapto-4-hydroxyphenyl)tetrahydrothiophene cadmium, tris-sulfonium sulfonic acid 1-(4-n-butoxyphenyl)tetrahydrogen Thiophene, trifluorosulfonium sulfonate (4-hydroxynaphthalen-1-yl)tetrahydrothiophene i, trifluorosulfonium sulfonate (4-oxaonaphthalen-1-yl)tetrahydrothiophene, trifluoroantimony Sulfonic acid benzoate (4-ethoxynaphthalen-1-yl)tetrahydrothiophene ί, tris, phthalic acid 1-(4-n-butoxynaphthalen-1-yl)tetrahydro fluorene, trifluoromethane Acid 1-(4-oxooxaonaphthalen-1-yl)tetrahydroporphyrin paste, trifluorosulfonium sulfonate (4-ethoxyoxonaphthalen-1-yl)tetrahydrothiophene, trifluorosulfonate Acid 1-[4-U-methoxyethoxy]naphthalen-1-yl]tetrahydrothiophene read, 1-[4-(2-oximeoxyethoxy)naphthalen-1-yl]tetrahydrofuransulfonate Thiophene rhyme,

C:\2D-CODE\91-09\91114303.ptd Page 100 1304060 V. INSTRUCTIONS (96) Nonafluoro-n-butyl phthalate 1-[4-(2-oxoethoxy)naphthalen-1-yl ] tetrahydro σ septene?: South, perfluoro-n-sphingoic acid 1-[4-(2-oxime oxyethoxy)naphthalen-1-yl]tetrahydro σ-septene 1, fluorite 1_(4-methoxyheptyloxynaphthalen-1-yl)tetrahydro sigma, trifluorosulfonium sulfonate (4-ethoxycarbonyloxynaphthalen-1-yl)tetrahydrothiophene, trifluorosulfonate Acid bromide (4-n-propoxycarbonyloxynaphthalen-1-yl)tetrahydrothiophene fluorene, trifluoromethane acid 1-(4-isopropoxy methoxynaphthalen-1-yl)tetrahydro σ septene , Tri-I-acid acid 1-(4-n-butoxy-methoxy-naphthalenyl-I-yl)tetrahydro-sodium sulfonate, trifluorosulfonium sulfonate (4-tertoxycarbonyloxynaphthalen-1-yl) Tetrahydrothiophene ore, trifluorosulfonium sulfonate (4- oxaphthalene-buyl) tetrahydrothiophene lysine, trifluorosulfonium sulfonate (2-naphthalen-1-yl-2-one ethyl) tetrahydrogen Thiophene, trifluoromethyl 1-[4-(2-tetrahydroindolyl)-naphthalen-1-yl]tetrahydro σ thiophene sieve, trifluorosulfonium sulfonate [4-(2-tetrahydropyran) Oxy)naphthalen-1-yl]tetrahydrothiophene _ and the like. &lt;Antimony compound&gt; Examples of the hydrazine compound include b-ketosulfone, b-sulfonylsulfone, and a-diazo compound of these compounds. Specific examples of the sulfone compound include benzoylphenyl sulfone, 2,4,6-trisylphenyl benzhydryl sulfone, bis(phenylsulfonyl)methane, and 4-paraben. Mercaptosulfone. <Sulfonate compound> Examples of the acid ester compound include a sucrose-saturated ester, a sulphuric acid ii, a sulphuric acid, a sulphuric acid, and an acid imide. As clear examples of the reductate compound, benzoin toluene, ester, gallic phenolphthalein trisulfonate, nitrobenzyl-9,10-diethoxy onion-2-sulfonate

C:\2D-CODE\91-09\91114303.ptd Page 101 1304060 V. INSTRUCTIONS (97) Acid ester, a-hydroxyindole benzoin tosylate, a-hydroxymethylbenzoin trifluorosulfonate Ester, a-hydroxyindole benzoin n-octyl sulfonate, a-hydroxyindole benzoin dodecyl sulfonate, and the like. <Disulfonyldiazomethane compound> Examples of the disulfonyldiazomethane compound include compounds represented by the following chemical formula (2 9 ): 〇Ν2 Ο 97丨丨丨丨丨1 27 R27—S—C—S—R27 (29) II 11 0 wherein R 27 represents a monovalent group such as an alkyl group, an aryl group, an alkyl halide group, and a halogenated aryl group, respectively. Specific examples of the disulfonic acid diazonium terbene compound include bis(trifluoromethanesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazonium, and bis(phenylsulfonyl). Diazononane, bis(p-phenylenesulfonyl)diazononane, bis(2,4-dimethylphenylsulfonyl)diazonium, sulfonyl-p-phenylenesulfonyl-diazo Methane, bis(4-t-butylphenylsulfonyl)diazomethane, bis(4-sulfosulfonyl)diazomethane, (cyclohexylsulfonyl)(p-toluenesulfonyl)diazodecane (cyclohexylsulfonyl) (1,1-dimercaptoethanesulfonyl) diazomethane,

C:\2D-CODE\91-09\91114303.ptd Page 102 1304060 V. INSTRUCTIONS (98) Bis(1,1-dimercaptoethanesulfonyl)diazononane, bis(1-indenyl) Ethylsulfonyl)diazononane, bis(3,3-dimercapto-1,5-di- 4-spiro[5.5]dodecane-8-sulfonyl)diazononane, double (1,4 _2 4 snail [4· 5] decane-7 sulfonyl) diazonium decane and the like. <Disulphonyl decane compound> Examples of the disulfonyl methane compound include compounds represented by the following chemical formula (30): R28-S-CS-R28 (30) 〇W 〇 R28 represents a linear or branched monovalent aliphatic hydrocarbon group, a cycloalkyl group, an aryl group, an aralkyl group, or another monovalent organic group having a hetero atom, and V and W represent an aryl group, a hydrogen atom, a straight chain or a branch, respectively. a chain monovalent aliphatic hydrocarbon group, or another monovalent organic group having a hetero atom, wherein the restriction is that at least one of V and W represents an aryl group, or V and W are bonded to form a single ring or more having at least one unsaturated bond. The cyclic ring, or the V and W bonds, form a group represented by the following chemical formula (3 1):

C:\2D-C0DE\91-09\91114303.ptd Page 103 1304060 V. Inventive Note (99) wherein V' and W' represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, or The aralkyl group, or V' and W', are each bonded to the same or different carbon atom bond to form a monocyclic carbon structure, and b is an integer from 2 to 10. <Sulphonic acid sulfonium compound> Examples of the sulfonic acid sulfonium compound include compounds of the following chemical formula (3 2 - 1) or (3 2 - 2 ): R29 〇I II , NC-C=N-〇-S- R30 (32-1) 〇0 R29 〇(32-2)

R30— S— ο— N—c— C=N— o—s— R30 II 129 H 〇R29 〇 wherein R29 and R3G represent a monovalent organic group, respectively, and when two R29 and R3G groups are present, such a group Groups can be the same or different. As a clear example of R29 in the chemical formulae (32-1) and (32-2), a mercapto group, an ethyl group, a n-propyl group, a phenyl group, a toluenesulfonyl group and the like can be given. As a clear example of R3G in the chemical formulas (32-1) and (32-2), a phenyl group, a pyrene sulfonyl group, a naphthyl group or the like can be given. <Sulphonic acid sulfonium compound> Examples of the sulfonic acid sulfonium compound include

C:\2D-C0DE\91-09\91114303.ptd Page 104 1304060 V. INSTRUCTIONS (100) Bis(phenyl)sulfonate, bis(p-phenylene)sulfonate, bis(trifluoroanthracene) Astragalus membranaceus, bis(nonafluoro-n-butane) sulfonium sulfonate, bis(n-propyl) hydrazine, benzenesulfonate, p-toluenesulfonate, trifluorosulfonium sulfonate, nonafluorobutanesulfonate , n-propionyl sulfonium, trifluorosulfonyl sulfonyl p-phenylene sulfonate and the like. Among these other acid generators, bis(t-butylphenyl)phosphonium trifluorosulfonate, bis(t-butylphenyl) ester of 10-camphorsulfonate, triphenylsulfonate triphenylsulfonate #U , 1 0 - cerebral acid triphenyl gas, N - (three gas 醯 醯 氧 oxy)-7 - 吟 bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, ^ (10-camphorsulfonyloxy) Amber quinone imine or the like is preferred. These other acid generators may be used singly or in combination of two or more. In the radiation-sensitive resin compositions (i) - (iii), for the total amount of the acid generator (I) and other acid generators of 100% by weight, the ratio of use of other acid generators is 90% by weight. Or preferably, and preferably 80% by weight or less. Although the positive type radiation sensitive resin composition (i), the positive type radiation sensitive resin composition (i i ), and the negative type radiation sensitive resin composition (i i i)

C:\2D-C0DE\91-09\91114303.ptd Page 105 1304060

The characteristics vary, but it is preferable that the ratio of the components of the invention (101) is as follows according to the desired ratio of the photoresist. For the positive type radiation sensitive resin composition (i) and the positive: fat composition (1)), for the m part by weight of the acid-containing cleavable group; the resin or the alkali soluble resin, the acid generator (1) The system ()ι_7 part is better in weight, 0 · 50 parts by weight is better, and 〇 · 5_2 parts by weight is particularly good. The amount of the acid generator (1) of less than 0.01 part by weight detracts from sensitivity and resolution. If the amount exceeds 70 parts by weight, the photoresist coating property f and the pattern form tend to be adversely affected.

For the positive-type radiation-sensitive resin composition (i丨), for 100 parts by weight of the alkali-soluble resin, the amount of the alkali solubility control agent is 5 - i 5 parts by weight, and 5 to 100 parts by weight is more Good, and 5_5 parts weight is particularly good. An amount of the alkali solubility control agent of less than 5 parts by weight reduces the residual coating rate and causes the pattern to swell. If the amount exceeds 150 parts by weight, there is a tendency that the surface of the coating becomes thick and the surface strength of the coating layer is lowered.

For the negative-type radiation-sensitive resin composition (i丨丨), the amount of the alkali-soluble resin is 1 part by weight, and the amount of the acid generator (1) is preferably 7 parts by weight, 〇·1 - 50 parts by weight is better, and 〇 · 5 - 2 parts by weight is particularly good. The amount of the acid generator (I) of less than 0.1 part by weight detracts from sensitivity and resolution. If the amount exceeds 70 parts by weight, the photoresist coating properties and pattern morphology tend to be adversely affected. For 100 parts by weight of the alkali-soluble resin, the crosslinking agent (p) is preferably added in an amount of from 5 to 95 parts by weight, more preferably from 15 to 85 parts by weight, still more preferably from 20 to 75 parts by weight. Amount of less than 5 parts by weight of the crosslinking agent (Ε) will reduce the residual coating rate and

1304060 .- V. Invention Description (102): It is intended to cause distortion and expansion of the pattern. Amount

There is a tendency for the developability of the exposure &amp; field to decrease. Shell J <Acid Diffusion Control Agent> Positive: ΐ The bismuth preparation is added to the positive radiation sensitive resin composition (1), and the iL f quinone composition (ι) and the negative susceptibility sensitive resin are preferred. The acid diffusion controlling agent controls the diffusion of the acid generated by the photoresist during the exposure to the photoresist, thereby preventing unfavorable chemical reactions in the unexposed regions. The addition of an acid diffusion controlling agent can improve the storage stability of the composition and the degree of resolution as a light agent. In addition, the addition of an acid diffusion controlling agent can prevent the photoresist pattern from being exposed to the post-exposure heat treatment exposure. A change due to post-delay (pED), whereby a composition having remarkably excellent processing stability can be obtained. Regarding the acid diffusion controlling agent, the nitrogen-containing organic compound whose alkalinity does not change during the exposure or heating of the photoresist pattern is preferable. Examples of such a nitrogen-containing organic compound include a compound represented by the following chemical formula (33) (hereinafter referred to as "nitrogen-containing compound (Q)"), R31 (33) R31 - Ν - R31 wherein R3, 1 Respectively represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, which is unsubstituted or substituted with a functional group such as a trans group. a diamine-based compound having two nitrogen atoms in the molecule (hereinafter referred to as "including

C:\2D-OODE\91-〇9\91114303.ptd Page 107 1304060 V. INSTRUCTIONS (103) Nitrogen compound (/3)"), diamine polymerization of three or more nitrogen atoms in the molecule (hereinafter referred to as "nitrogen-containing compound (7)"), a guanamine-containing compound, a urea compound, and a nitrogen-containing heterocyclic compound. Examples of the nitrogen-containing compound (α) include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, and n-decylamine; dialkylamines such as di-n-butylamine, di-n-pentylamine, and n-Hexylamine, di-n-heptylamine, di-n-octylamine, di-n-decylamine, and di-n-decylamine; trialkylamines such as triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine , tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, and tri-n-decylamine; and aromatic amines such as aniline, anthracene-nonylaniline, anthracene, fluorenyl-diphenylaniline, 2-mercaptoaniline, 3-mercaptoaniline, 4-mercaptoaniline, 4-n-aniline, diphenylamine, triphenylamine, and 1-naphthylamine. Examples of the nitrogen-containing compound (/5) include ethylenediamine, hydrazine, hydrazine, hydrazine, Ν' _tetradecylethylenediamine, hydrazine, hydrazine, hydrazine, Ν'-肆 (2-hydroxypropyl) Diamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylnonane, 4,4'-diaminodiphenyl ether, 4,4'-diamine Diphenyl ketone, 4, 4'-diaminodiphenylamine, 2,2' • bis(4-aminophenyl)propane, 2-(3-aminophenyl 2-(4-aminophenyl)propene , 2-(4-aminophenyl)-2-(3-phenyl)propane, 2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane, 1,4-double [1-(4-Aminophenyl)-1-indenylethyl]benzene, and 1,3-bis[1-(4-aminophenyl)-1-indenylethyl]benzene. Nitrogen-containing compound Examples of r) include polyethyleneimine, polyallylamine, diammonium ethyl acrylamide, etc. Examples of the guanamine-containing compound include guanamine, N-mercaptoamine, N , N-dimercaptoamine, acetamide, N-mercaptoacetamide, N,N-dimethylacetamide, acetamide, benzoguanamine, pyrrolidone, and N- Mercaptopurine

C:\2D-CODE\91-09\91114303.ptd Page 108 1304060 V. INSTRUCTIONS (104) Examples of ketone oxime compounds include urea, alpha vein, 1,1_two veins, 1,3 - two Urea urea, 1,1,3,3-tetraguanazone, 1,3-diphenylurea, and tributylthiourea. Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, 4-mercaptopurine, 4-mercapto-2-phenyl 11 m squat, benzo sigma and 2-phenyl benzo s ° ° ratio σ class such as ° σ set, 2 - 曱吼 17 set, 4 - A ratio σ, 2 - 吼 吼 定, 4 - 吼 吼 定, 2 - benzene ratio 、, 4 - benzoquinone sigma, Ν-methyl-4 benzoquinone ratio σ, test, acid test, test guanamine, 琳琳, 8-oxoline, and ρ, / σ 定; ρ ratio. Sitting, tower. Well, scorpion, scorpion, scorpion, hexahydro hydrazine, morphine, 4-methyl phenanthrene, hexahydro ρ plough, 1,4 - dimethyl hexahydro 吼 σ well, 1, 4 - Diterpene bicyclo [2 · 2 · 2 ] octane, phenanthroline and the like. A nitrogen-containing compound having an acid cleavable group can also be used as the nitrogen-containing organic compound. Examples of the nitrogen-containing compound having an acid cleavable group include fluorene-(t-butoxycarbonyl)hexahydroacridine, fluorene-(t-butoxycarbonyl)imidazole, fluorene-(t-butoxycarbonyl) Benzimidazole, hydrazine-(t-butoxycarbonyl)-2-phenylbenzimidazole, hydrazine-(t-butoxycarbonyl)dioctylamine, hydrazine-(t-butoxycarbonyl)diethanolamine, hydrazine- (Third butoxycarbonyl) dicyclohexylamine, hydrazine-(t-butoxycarbonyl)diphenylamine, and the like. Among these nitrogen-containing organic compounds, a nitrogen-containing compound (α), a nitrogen-containing compound (stone), a nitrogen-containing heterocyclic compound, a nitrogen-containing compound having an acid cleavable group, and the like are preferable. The acid diffusion controlling agents may be used singly or in combination of two or more. 100% by weight of acid-soluble cleavable group resin or alkali soluble tree

C: \2D-OODE\91-09\91114303.ptd Page 109 1304060 V. INSTRUCTIONS (105) The amount of the acid diffusion control agent is usually less than 15 parts by weight, with 0 · 〇〇1 - 10 parts by weight is preferred, and 〇. 〇〇 5 - 5 parts by weight is better. If the ratio of the acid diffusion controlling agent exceeds 15 parts by weight, the sensitivity as a photoresist and the developability in the exposed region tend to be lowered. If the amount is less than 〇. 001 parts by weight, the pattern shape or dimensional accuracy of the photoresist will be reduced depending on the processing conditions. <Soluble-Soluble Resin> An alkali-soluble resin (hereinafter referred to as "alkali-soluble resin (c)") may be added to the positive-type radiation-sensitive resin composition (i) as needed. Examples of the alkali-soluble resin (c) include poly(4-hydroxystyrene), partially hydrogenated poly(4-hydroxystyrene), poly(3-hydroxystyrene), and partially hydrogenated poly(3- Hydroxystyrene), 4-hydroxystyrene/3-hydroxystyrene copolymer, 4-hydroxystyrene/styrene copolymer, novolac epoxy resin, polyvinyl alcohol, polyacrylic acid, and the like. It is preferable that the Mw of the soluble resin (c) is 1,0 0 0-1, 0 0 0, 0 0 0, and 2, 〇〇〇-1 〇 0,0 0 0 is preferable. These alkali-soluble resins (C) may be used singly or in combination of two or more. The amount of the alkali-soluble resin (C) added is preferably 30 parts by weight or less based on 100 parts by weight of the acid-containing cleavable group-containing resin. <Surfactant> A surfactant exhibiting a coating property or a line of an improved composition and a developability as a photoresist can be added to the positive radiation sensitive resin composition (i), positive radiation sensitivity Resin composition (ii), and negative radiation sensitivity

Page 110 C:\2D-C0DE\91-09\9llM303.ptd 1304060 V. INSTRUCTIONS (106) Inductive resin composition (i i i ). Examples of such surfactants include polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl oleyl ether, polyoxyethylidene octyl phenol ether, polyoxygen extension Ethyl n-decyl phenol ether, polyethylene glycol dilaurate, polyethylene glycol distearate; and commercially available products such as FTOP EF301, EF303, EF3 5 2 (manufactured by TOHKEM PRODUCTS CORPORATION), MEGAFAC F171, F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surf Ion S-3 82, SC-101, SC-102, SC-103, SC-104 , SC-105, SC-106 (manufactured by Asahi Glass Co., L td ·), KP 3 4 1 (S hi η - E tsu C hemica 1 C o ·, manufactured by L td ·), and Polyflow No. 75, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.). These surfactants may be used singly or in combination of two or more. The resin or the alkali-soluble resin having 100 parts by weight of the acid-cleavable group is preferably used in an amount of 2 parts by weight or less. <Sensitizer> A sensitizer may be added to the positive type radiation sensitive resin composition (i), the positive type radiation sensitive resin composition (ii), and the negative type radiation sensitive resin composition (iii). Examples thereof include carbazole, diphenyl ketone, bengal rosin, onion, and the like. These sensitizers may be used singly or in combination of two or more. 100 parts by weight of resin containing acid cleavable group or soluble resin, sensitizer

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5. The amount of addition of the invention (107) is preferably 50 parts by weight or less. <Other Additives> A latent image of the exposed area. Adhesive aids may be added. In addition, dyes and/or pigments may be added to visualize and reduce the halo effect during exposure to improve adhesion to the substrate. For other additions, a halo inhibitor such as 4-hydroxy-4-, methicone, a morphological modifier, a storage stabilizer, an antifoaming agent and the like can be added. Solvent

The positive type radiation sensitive resin composition (1) and the positive type (four) sensitive resin composition, (1 1), and the negative type radiation sensitive resin composition (丨丨丨) are used as a composition bath. 2毫米之间。 The composition is dissolved in a solvent, the total solid concentration is 〇 卜 〇 〇 〇 〇 〇 〇 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 毫米 毫米 毫米 毫米 毫米Prepared by a filter of pore diameter. Examples of the solvent used in the preparation of the composition solution include: ethylene glycol monoalkyl ketone acetate such as ethylene glycol monodecyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol single positive Propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate;

Propylene glycol monoalkyl ether such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and propylene glycol mono-n-butyl ether; propylene glycol dialkyl ether such as propylene glycol dimethyl ether, propylene glycol diethyl Ether, propylene glycol di-n-propyl ether, and propylene glycol di-n-butyl ether; propylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ketone acetate, propylene glycol single positive Propyl ether acetate, and propylene glycol

IB mm _ circle page 112 C:\2D-C0DE\91-09\9lll4303.ptd 1304060 V. Description of invention (108) Mono-n-butyl ether acetate; lactate such as lactic acid 曱S, ethyl lactate , n-propyl lactate, and isopropyl lactate; aliphatic carboxylic acid esters such as n-amyl decanoate, isoamyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate Ester, acetic acid, pentane acetate, isoamyl acetate, propionic acid isopropyl S, propionate n-butyl s, and isobutyl propionate; other esters such as ethyl hydroxyacetate, 2-hydroxy-2-mercaptopropyl Ethyl acetate, 2-hydroxy-3-indolyl decanoate, ethyl oxime acetate, ethyl ethoxyacetate, decyl 3-oxopropionate, ethyl 3-oxopropionate, 3-ethyl Methyl oxypropionate, ethyl 3-ethoxypropionate, butyl 3-oxime oxyacetate, butyl 3-methyl-3-indoleoxyacetate, butyl 3-mercapto-3-oxopropionate, Butyl 3-mercapto-3-methoxybutanoate, decyl acetate, ethyl acetate, pyruvic acid, and ethyl pyruvate; aromatic hydrocarbons such as toluene and diphenyl; ketones such as Methyl ethyl ketone, mercapto propyl ketone, decyl butyl ketone, 2-heptanone, 3-heptanone 4-heptanone, and cyclohexanone; guanamine such as N-mercaptoamine, N,N-didecylamine, N-mercaptoacetamide, N,N-dimercaptoacetamide And N-decylpyrrolidone; and internal such as g-butane S and the like. These solvents may be used singly or in combination of two or more. Formation of the photoresist pattern The composition solution prepared as described above is applied to a substrate such as by using a suitable coating method such as spin coating, cast coating, and recoating.

C:\2D-CODE\91-09\91114303.ptd Page 113 1304060 V. INSTRUCTIONS (109) 矽 Wafer or covered aluminum wafer forms a photoresist coating and consists of a positive sensitive resin The composition (1), the positive-type radiation-sensitive resin composition (1, , and the negative-type radiation-sensitive resin composition (lil) form a photoresist pattern. Then, if necessary, the photoresist is coated at about 7 〇. - pre-baking at a temperature of 6 〇t (hereinafter referred to as "PB"), and exposing to the light side through a predetermined mask pattern: examples of radiation used herein include deep ultraviolet light such as ultraviolet light, KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength nanometer) excimer laser (wavelength: 157 nm), or w (polar 钿1 external light 'wavelength: 13 nm) , charged particle rays such as electrons f, X-rays such as synchrotron radiation, deep ultraviolet light and electrons: exposure conditions such as exposure are based on the composition of sensitive resin, and the type of additives, additives, etc. And appropriately decided. ', after 7 〇 -16 ° ° C for post-exposure baking (hereinafter referred to as For &amp; Μ ^ ^ or above, consistently form a tiny brilliance with high precision = ΐ If the heating temperature of PEB is lower than 70 °c, the sensitivity will fluctuate depending on the type of substrate. The developer is preferably 15 to 100 seconds at 1 to 5 Torr, and preferably 15 to 90 seconds at 20 to 2 5 ° C to develop the photoresist to obtain a desired photoresist. Pattern: water-based ammonia, mono-di- or tri-alkylamine 1 = inspective, shadowing agent, can be used via (iv) such as metal hydroxide, single or triple-burn to 1-10 weight percent I, or 1 , 5 - diterpene bicyclo [4 · 3 · 0] - 5 - terpene dissolved in a hundred percent ratio, preferably 5 weight percent, and 3 weight

1304060 - - «ΜΜ-Η V. Description of invention (110) ί: An alkaline aqueous solution prepared by the concentration of ΐ. In addition, the appropriate amount of , six ® ^ ^ #1 ^ ^ ^ α ± IJ J ^ ^ ^ when forming a photoresist pattern, can be -:: 蒦 film: Qiao: medium. ί ':: stop i is in the ambient atmosphere: ΐΐί: agent coating = outside, the anti-reflective film can be placed in the lower layer or the adverse effects of the present invention will be explained by the example of this invention. Ping fine conditions. However, % should not be equal to this and two t: Unless otherwise indicated, the parts and % refer to the parts by weight of the acid production agent (I 丄 免 成 合成 合成 合成 合成 合成 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ The bath of dicyclopentadiene and 322·4 g of bromomethyl is added to the autoclave as a polymerization inhibitor, and the mixture is mixed. (: The next mixing is 5 hours. 8 generations and 25 milli"" retort, the reaction product was purified to obtain 32 6 grams of bromotetrafluoro-2-(dehydrourethane-5-ene-2-yl)ethane clear liquid (by U- a)"). Next, a solution of 62 g of the compound (1-a) dissolved in 1 liter of ethyl acetate was added to a 2 liter eggplant-shaped flask, and 12 g of 5% hydrazine was added. After the alumina, the mixture was vigorously stirred in a hydrogen atmosphere for 3 hours. The reaction solution was then filtered under reduced pressure through a glass filter covered with diatomaceous earth. Filter mm Page 115 C:\2D.mDE\91- 09\91114303.ptd 1304060 V. Inventive Note (ill) '-- ----- n' minus 1 'shrinking, and purifying the reduced product by distillation under reduced pressure (hereinafter referred to as "compound" (1_b)") 1 of which A 2 liter three-necked flask in which the atmosphere was completely replaced by nitrogen was charged with 7 g of sodium sulfite and 52 g of sodium hydrogencarbonate dissolved in 3 ml of water. Then, (10) ml of 55 g of compound (b b) was dissolved. The solution of acetonitrile was added by dropwise addition to the chamber for 1 hour, and the solution was allowed to react at 75 ° for 2 hours. After evaporating under reduced pressure, 35 () mg of sodium tungstate dihydrate and 5% of the acid monohydrogen soda. Add 5.6 ml of 3 aqueous hydrogen peroxide solution by adding dropwise to the temperature, while carefully maintaining one of the reaction solutions. The water was removed, the residue was extracted with methanol and distilled under reduced pressure to remove methanol, thus yielding 35 g of yt, 2, 2,4-tetrafluoro-2-mono(de-indol-2-yl)ethanesulfonic acid Sodium (hereinafter referred to as "compound (ic)"). Next, '80 g of 1-n-butoxynaphthalene and 212 g of phosphorus pentoxide-methanesulfonate are added to a 5 liter eggplant-shaped flask, and The mixture was stirred at room temperature for 15 minutes. 47 g of tetradecylene sulfoxide was added to the mixture by dropping in 〇t and the mixture was stirred for 2 minutes. Then, the temperature of the mixture was gradually increased to room temperature. The mixture was further stirred for 1 hour. The mixture was again cooled to G ° C ° after adding 2 liters of water and adjusting the pH to 7β 25 using 25 ° / aqueous ammonia. 'The mixture was stirred at room temperature for 1 hour. After adding 1 16 g of the compound (1-c) to a solution of 150 ml of water, the mixture was further stirred at room temperature for 1 hour. The reaction solution was extracted with an alkane, and the extract was washed with water. The methylene chloride was evaporated under reduced pressure, and the residue was purified using a silica gel column (dichloromethane: decyl alcohol = 20:1). By using dioxane / hexane

C:\2D-CODE\9l-09\91114303.ptd第116页

1304060 V. INSTRUCTIONS (112) ' ' -- Reprecipitation, and obtained 76 grams of 1,1,2,2-tetrafluoro-2-(dehydro-2-yl)ethanesulfonic acid 1,4 - Butyl n-butoxynaphthalene _4-base). The results of 1 H-NMR analysis of this compound are shown in Fig. 1. The mass analysis results of the cationic group and the anionic group are shown in Figures 2 and 3, respectively. This compound is referred to as "acid generator (A_丨)". The mass analysis of the acid generator (A-1) and the following acid generators (A-2) to (A-6) was carried out according to the following conditions: Apparatus: JMS-AX5 05W mass spectrometer (manufactured by JEOL, Ltd.) ) Transmitter current · · 5 mA (using gas · · Xe ) Accelerating voltage : 3 · 〇仟 ION MULTI : 1. 3 Ionization method : Fast atom bombardment (FAB ) Detecting ions : cation ( + ) Measurement quality Range: 20-1500 m/z Scan: 3 G seconds Resolution: 1 5 0 0 Matrix: 3 - Shisaki Benzyl Alcohol Synthesis Example 2 2 liters of the Soviet-shaped flask was poured into 2 g of gasified triphenylbenzene dissolved in 5 〇〇ml of water solution. An aqueous solution containing 2 gram of the compound (1 -d) was added dropwise thereto at room temperature, and the mixture was stirred for 3 minutes. The reaction solution was extracted with ethyl acetate and the organic layer was washed twice with water. The clarification and high viscosity of 1,6 g of 1,1,2,2 _tetrafluoro-2 -(nor-on- 2 -yl)-ethene κ acid was obtained by steaming the solution under reduced pressure. oil. u M R of this compound

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Page 117 1304060 V. Description of invention (113)

The results of the analysis are shown in Fig. 4. The cations of the 囿u team A are shown in Figures 5 and 6, respectively. Mass analysis of the group and the anionic group This compound is referred to as "acid generator (A-2). Synthesis Example 3". A 2 liter incised flask was placed in a 2 \ 溶液 solution. The β aqueous solution was added to the mixture by adding an aqueous solution of U-c) containing 1 liter of water at room temperature and passing the mixture to 20 g of the compound and ruthenium through a glass filter. The results of the analysis of 12 gram of 1,1,2,2-tetrafluoro-2_(de; 葙'; '5:= under dryness are shown in Fig. 7. Cationic group and _ ionic group The results of the mass analysis are shown in Figures 8 and 9, respectively. The compound is referred to as "acid generator (Α-3). Synthesis Example 4 2 thiodithioate and 52 which are completely replaced by nitrogen in the atmosphere = 52 a solution of gram of sodium bicarbonate in a solution of milliliters of water; 30 ml of 55 g of compound (1.), and six recognizable 7 ★ will be dripped into the hour and force... and make:::/7夂 of the chemical solution The mixture was reacted at 75 ° C for 2 hours at room temperature. After the acetonitrile was evaporated under reduced pressure, the reaction solution was extracted with acetic acid. The layer was washed with saturated brine and dried over anhydrous sulfuric acid. The magnesium was dried and evaporated under reduced pressure to give 35 g of 1,1,2,2-tetrafluoro-2-(sodium-decarboxyl-2-ylethanesulfonate (hereinafter referred to as "compound (1 - ). Down, '2 liters of sulphate into a solution of 8 gram of compound (η) dissolved in 2-50 ml of water. Stir at room temperature, foam more than 1 5 with excess chlorine. Minutes to methylene chloride Take on the bottom of the flask collected

1304060 V. Oily substance of invention (114). The organic layer was washed with a sodium hydrogencarbonate aqueous solution and dried over anhydrous magnesium sulfate. The methylene chloride was evaporated under reduced pressure to obtain 6 8 g of 1,1,2,2-tetrafluoro-2-(nor-methyl-1-yl)ethanesulfonyl chloride (hereinafter referred to as "compound (4). -a)"). Next, '22 g of N-light-based-5-nor-boxene- 2,3-dioxalic acid sub-monthly female to 30 g compound (4-a) dissolved in 1 5 g of tetrahydro-sigma After the solution was stirred, 29 g of triethylamine was added to the mixture via dropwise addition. After the reaction solution was stirred at room temperature for 10 minutes, water was added dropwise thereto to obtain a white crystal of the reaction product. After filtration, the crystals were dissolved in dichloromethane, and the solution was successively washed with an aqueous sodium hydrogencarbonate solution, an aqueous oxalic acid solution, and water. After the solution was dried over anhydrous sulphuric acid, dichloromethane was evaporated under reduced pressure to give &lt;RTI ID=0.0&gt;&gt; Ethylene sulfonate)-5-nor-methene-2,3-dicarboxyarmine. Figure 10 shows the results of iH-nmr analysis of this compound. This compound is referred to as "acid generator (A _ 4 )". Synthesis Example 5 An autoclave was charged with 108.5 g of dicyclopentadiene and 322.4 g of bromo-1,1,2,2-dimethyl-3-butene. 0. 3 g of 4-oxophenol was dissolved in 5 ml of benzene in benzene, and the solution was added to a autoclave as a polymerization inhibitor, and the mixture was stirred at 170 ° C for 5 hours. The product was purified by distillation under reduced pressure at 85 ° C and J mm Hg to give 226 g of bromo-indole, hydrazine, 2,2-tetrafluoro-2-(tetracyclic [4.4.0.12] , 5.17, 1 〇] dodecane-3-ene-8-yl) ethane liquid (hereinafter referred to as "compound (5 - a)"). Next, 93 g of the compound (5-a) was dissolved in 丨·5 liter of ethyl acetate.

Page 119 1304060 V. INSTRUCTIONS (115) The solution is added to a 3 liter eggplant-shaped flask. After 18 g of 5% cerium oxide containing aluminum oxide was added, the mixture was vigorously stirred in a hydrogen atmosphere for 3 hours. The reaction solution was then filtered under reduced pressure through a glass filter covered with diatomaceous earth. The filtrate was concentrated under reduced pressure, and the concentrate was purified by distillation under reduced pressure to give 85 g of 1-bromo-1,1,2,2-tetrafluoro- 2- (tetracyclo[4. 4·0· I2,5·17,丨°] 12-burn-8-yl) ethane clear liquid (hereinafter referred to as "compound (5 - b)") A 2 liter three-necked flask in which the atmosphere is completely replaced by nitrogen. Into 1 〇. 2 g of monothiosodium hydride and 7.4 g of sodium bicarbonate dissolved in 1 7 ml of water. Then, 10 g of the compound (5 - b ) &gt; solution was added to the solution of 750 ml of B-epi by dropwise addition at room temperature for 1 hour, and the solution was allowed to react under hydrazine for 7 hours. After acetonitrile was allowed to stand, the aqueous solution was filtered and the filtrate was concentrated under reduced pressure. The residue was extracted with decyl alcohol and distilled under reduced pressure to remove sterol, thus yielding 10.2 g of 1,1,2,2-tetrafluoro-2-(tetracyclo[4.4.〇12,517'1〇] twelve Sodium 8-ethyl sulfinate (hereinafter referred to as "compound (5-c)) Next, a 500 ml three-necked flask was charged with a solution of 9 g of the compound (5-c) dissolved in 75 ml of water. 50 mg of sodium tungstate dihydrate and 2 g of disodium hydrogen phosphate. Add 3 ml of 30% aqueous hydrogen peroxide solution by adding dropwise to the chamber while carefully maintaining the reaction solution. Add 60 ml of water at 6 (TC Η ', and let the mixture cool: room temperature. Then add 1 g of gasified trisulphur in 250 ml of water and add dropwise to the solution at room temperature. The reaction solution was stirred for 1 hour. Next, the reaction solution was extracted with acetic acid, and the organic layer was washed three times with water.

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Page 120 1304060 V. INSTRUCTIONS (116) Ethyl acetate was removed under reduced pressure, and the residue was purified using a silica gel column (dichloromethane·methanol 2 8 ··1) , 2, 2-tetrafluoro-2 —(tetracyclo[4·4· 0· 1 ' · 1''ig ] dodecane-8-yl) triphenyl sulfonate. The results of H-NMR analysis of this compound are shown in Fig. 11. The mass analysis results of the cationic group and the anionic group are shown in Fig. 2 and Fig. 3, respectively. This compound is referred to as "acid generator (A-5)". Synthesis Example 6 A 2 liter eggplant-shaped flask was charged with 25.2 g of sodium hydrogencarbonate dissolved in 5 (10) mM. While stirring the solution at room temperature, 2-(oxasulfonyl)difluoromethyl acetate of B was added dropwise thereto. Then mix it with ^ 1 · stir for 2 hours, then reduce the water base σ under reduced pressure; then go to the middle name palace, w hong π — , and make the solids in the straight work Drying the partition, passing through 2 ml of methanol, and drying in a vacuum at room temperature to obtain 〇·34 g of 甲其一# sodium decane sulfonate (hereinafter referred to as "compound (6 - a) "). Back soil, monofluoride Next, ’ 4 78 g of gasified triphenyl hydrazine was dissolved in 5 ml of water 6. 0.34 g of compound (6-a) was dissolved in 15 ml of water. This mixed solution was extracted twice with hydrazine to ethyl acetate. The organic layer was taken up in 2 mL of EtOAc and dried over anhydrous sodium sulfate. The product was removed by evaporation under reduced pressure, and the residue was dried in vacuo to give </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; Further, the cationic group and the anionic group of the compound are shown in Figs. 14 and 15. The results of the Berry knife analysis are referred to as "acid generator (A-6)". Synthesis Example 7

C:\2D-CODE\91-09\91114303.ptd 1304060

Fluor-2-(dehydro-2-yl)ethanesulfonate (4-hydroxy-3, 5) 2 liters of flask shaped into 2 gram of sucrose (4_经基_3,5_ - mercaptophenyl) tetrahydrofuran is dissolved in 5 ml of water. 5 ml of an aqueous solution containing 20 g of compound (lc) is added dropwise at room temperature to add and give the mixture Mix for 15 minutes. Filter the crystal of the chamber through the glass: and dissolve in the methylene chloride. Add the solution to the hexane by dropwise addition: Wait for the white precipitate. The precipitate will be filtered again through the glass filter: The collected solid is dissolved in acetone, and a white precipitate is obtained by dropping into the hydraulic port to the crucible. The precipitate is again filtered through a glass filter, collected, and dried under reduced pressure. "克之丨,丨,2,2—four n -ti· \ — αχ _. ^ 5 J 5 tetrahydrothiophene | dimercaptophenyl) Figure 16 shows the results of 1H-NMR analysis of this compound. The compound is referred to as "acid generator (A-7)". Jin Chengjing Example 8 a A 2 liter eggplant-shaped flask was charged with 2 g of the compound (1-c) in a solution of a methanol/water (70/30) mixed solvent. While stirring the solution at room temperature, 36 g of bis(4-t-butylphenyl) sulfate was added via dropwise addition to a solution of 1 liter of decyl alcohol. The mixture was then mixed at room temperature for a small % and allowed to stand for 1 day. The organic matter in the reaction solution was extracted with dichloromethane. The organic layer was washed with water and dried over anhydrous magnesium sulfate. The product was dissolved in dichloromethane, and the solution was added to the oxime via dropwise addition to obtain a white body. The crystal was filtered through a glass filter and dried under reduced pressure to obtain 18 g of 1,1,2,2-tetrafluoro-2-(de-t-butyl-2-yl)ethanesulfonic acid bis (4 wide second Butyl phenyl) iron. Figure 1 7 shows the results of the 1 Η - N M R analysis of this compound.

1304060 - ~ - -_ V. Description of the Invention (118) This compound is referred to as "acid generator (A-8)".

厶忐 Synthesis of box acid crackable resin Example Q 1 gram of 4-acetoxystyrene, 5 grams of styrene, 42 grams of 4 a second butoxide oxygen, 6 grams of azobisisobutyronitrile ( AIBN), and 1 gram of the third-undecyl mercaptan are dissolved in 丙6 gram of propylene glycol monoterpene ether. The mixture was polymerized in a nitrogen atmosphere at 70 C for 6 hours. After the polymerization, the reaction solution was added dropwise to a large amount of n-hexane to coagulate and purify the resulting resin. After adding 150 grams of propylene glycol monomethyl ether to the resin, 3 〇 〇 曱 酉 、 hand, 80 grams of triethylamine, and 5 grams of water were added. The mixture was hydrolyzed for 8 hours while refluxing at the boiling point. After the reaction, the solvent and triethylamine were stripped under reduced pressure. The resulting resin was dissolved in acetone, and the solution was added dropwise to a large amount of water to agglomerate the resin. The resulting white powder was filtered and dried under reduced pressure at 5 〇 〇 c overnight. The Mw and Mw/Mn of 16, 〇〇〇 and 1.7, respectively, were measured. The results of 13C_NMR analysis confirmed that the copolymer had a copolymerized molar ratio of 4-hydroxystyrene, styrene, and 4-tert-butoxystyrene of 72:5:23. This resin is referred to as "resin (B - 1 )". Mw and Μ of the resin (B-1) and the following resins (B-2) to (B-13) were subjected to gel permeation chromatography (GPC) using a GPC column (manufactured by Tosoh Corρ., G2 0 0HXL) X 2, G3 0 0 0HXL X 1, G4 0 0 0HXL X 1) Measured under the following conditions. Flow rate: 1 · 〇 ml / min, eluent: tetrahydroanthracene, column temperature: 40 ° C, standard reference material: monodisperse polystyrene. Synthesis Example 1 0

C:\2D-TODE\91-09\91114303.ptd Page 123 1304060 V. INSTRUCTIONS (119) 100 g of 4-ethoxixystyrene, 25 g of tributyl acrylate, 18 g of styrene, 6 Ake IBN, and 1 gram of the third-dodecylmercaptan are dissolved in 230 grams of propylene glycol monoterpene ether. The mixture was polymerized in nitrogen atmosphere at 7 Torr for 16 hours. After the polymerization, the reaction solution was added dropwise to a large amount of hexane to coagulate and purify the resulting resin. After adding 150 g of propylene glycol monoterpene ether to the resin, 3 gram of sterol, 80 g of diethylamine, and 15 g of water were added. The mixture was hydrolyzed for 8 hours while refluxing at the boiling point. After the reaction, the solvent and triethylamine were evaporated under reduced pressure. The resulting resin was dissolved in acetone, and the solution was added dropwise to a large amount of water to agglomerate the resin. The resulting white powder was filtered and dried under reduced pressure at 5 〇 〇 c overnight. The resins were found to have Mw and Mw/Mn of 11,50 0 and 1.6, respectively. The results of 13C-NMR analysis showed that the copolymerized molar ratio of 4-benzazole copolymer 4, styrene, acrylic acid, and styrene was 61:19:20. This resin is referred to as "resin (B-2)". Synthesis Example 11 176 g of 4-tert-butoxystyrene was anionically polymerized at -78 in 5 ml of tetrahydrofuran using n-butyllithium as a catalyst. After the polymerization, the resulting resin solution was coagulated in decyl alcohol to obtain 5 g of white poly(4-tert-butoxystyrene). 150 g of hydrazine (4_2,2,2-butoxyethylene) was dissolved in 6 g of dioxin. After the addition of dilute hydrogen acid, the mixture was hydrolyzed at 7 ° t for 2 hours. The reaction product was added dropwise to a large amount of water, thereby agglomerating the resin. Repeatly dissolving the resulting resin in C-S and adding it to a large amount of water to make the tree

1304060 V. Invention Description (120) &quot;&quot;1&quot; The resulting white powder was filtered and dried overnight under 5 dances. i The Mw and Mw/Mn of the resin are 10, 400 and 1.0, respectively. NMR analysis confirmed that only a portion of the third butyl group in the poly(4-tert-butoxystyrene) has a hydrolyzed structure, and the molar ratio of 4-t-butoxystyrene and 4-hydroxystyrene is 6 8 :32. "," This resin is called "resin (B-3)". Synthesis Example] 2 25 g of a copolymer of 4-hydroxystyrene and 4-tert-butoxystyrene (copolymerized molar ratio, 90:10) was dissolved in 1 gram of n-butyl acetate. Allow the atmosphere to foam through the solution for 30 minutes. After adding 3 · 3 g of ethyl ethyl squarate and i g of p-toluenesulfonic acid pyridine as a catalyst, the mixture was allowed to react at room temperature for 12 hours. The reaction solution was added dropwise to a 1% aqueous ammonium solution to cause agglomeration of the tree. The resin was filtered and dried overnight at 5 ° C in a vacuum desiccator. 〇1。 The Mw and Mw/Mn of the resin are 1, 3, 0 0 and 1. 〇1, respectively. From the results of uc-NMR analysis, it was determined that the resin had a molar ratio of 23 valence of 77 phenols in the poly(4-hydroxystyrene) group via ethoxyethyl group, and the percentage of 丨〇mol = Tributyl substituted structure. ί This resin is called "resin (β - 4 )". Synthetic solid package &lt;column 1 3 5 g of the norm is diluted, 11 g of cis-butylic acid anhydride, 11 g of 8 - sono-based tetracyclic [4.4.0.12'5.17'1〇] twelve;): End _ 3-dilute, and 23 g of methyl methacrylate 2-mercapto-2-adamantyl ester is dissolved in 50 g of tetrahydrofuran, and the average

1304060 V. Description of invention (121) Hook/Valley 'Night. After immersing in nitrogen for 30 minutes, 3 grams of A IBN was added. The mixture was heated to 65 ° C and stirred at this temperature for 6 hours. After the polymerization, the solution was allowed to cool to room temperature and diluted with 50 g of tetrahydrofuran. The diluted solution was poured into 1, (10) liters of n-hexane. The precipitated white powder was collected by filtration and dried to give a resin. This resin has nordecene·maleic anhydride··8-hydroxytetracyclo[4·4·0·12′5·17′10]dodec-3-ene··mercaptoacrylic acid 2 - Mercapto-2-Golden vinegar = 1 5 ·· 3 5 ·· 2 0 : 3 0 copolymerization ratio of copolymer with a M of 6,1 0 0 This resin is called "resin (Β —5)”. Synthesis Example Ί 4 46. 31 g of decylacrylic acid 2-indenyl-2-amantane and 53. 69 g of the following compound (34) were dissolved in 200 g of 2-butanone to give a homogeneous solution. Subsequently, 4.04 g of decyl bis-isovalerate was added as an initiator to obtain a monomer solution. Nitrogen gas was bubbled through a 1 liter three-necked flask containing 100 grams of 2-butanone for 30 minutes. Increase the temperature to 8 〇 t while stirring. The above monomer solution was added by dropping at a rate of 1 〇 ml / 5 minutes, and the mixture was polymerized for 5 hours. The reaction solution was cooled to 3 liters or less and poured into 2,0 gram of methanol. The resulting white precipitate was collected via filtration, mixed with 400 g of methanol and washed twice. The white precipitate was filtered and dried at 50 ° C for 17 hours to obtain a resin. This resin has 2-methyl-2-anoic acid methacrylate: the compound of the formula (1)^^^^彳 has a copolymerization ratio of ^(10)

C:\2D-00DE\91-09\91114303.ptd 1304060 V. Inventive Note (122) Copolymer. This resin is called "resin (B-6) H2 CH3II clclcl〇 (3

〇 Synthesis Example 1 5 40. 90 g of mercaptopropyl 2-methyl-2-amantane, 15.47 g of decylacrylic acid 3-yl-1-adamantyl ester, and 43·64 g The compound of the formula (34) was dissolved in 200 g of 2-butanone to obtain a homogeneous solution, followed by the addition of 4.02 g of azobisisovalerate to obtain a monomer solution. Nitrogen gas was bubbled through a 1 liter three-necked flask containing 100 grams of 2-butanone for 3 minutes. Increase the temperature to 8 〇t with stirring. The above monomer solution was added by dropwise addition at a rate of 1 ml / 5 minutes, and the mixture was polymerized for 5 hours. The reaction solution was cooled to 30 t or less, and poured into methanol of 2,0 g. The resulting white precipitate was collected via filtration, mixed with 40 g of sterol and washed twice. The white precipitate was filtered and dried at 50 ° C for 1 hour to give a resin. This resin has 2-methyl-2-adamantyl methacrylate: 3-hydroxy-1_adamantyl methacrylate · Compound of formula (34) = 36·2: 1 5 · 2 ·· 4 The copolymerization of 8 · 6 is a copolymer having a Mw of 9,200.

C:\2D-OODE\91-O9\91114303.ptd Page 127 1304060 V. INSTRUCTIONS (123) This resin is referred to as "resin (B-7)". Synthesis Example 1 6 50. 55 g of 2-mercapto-2-oxanyl methacrylate, 25.49 g of 3-hydroxy-1-carbo- methacrylate, and a chemical formula of 23·97 g ( The compound of 34) was dissolved in 200 g of 2-butanone to obtain a homogeneous solution, followed by the addition of 3.9 g of methyl azobisisovalerate to obtain a monomer solution. Nitrogen gas was bubbled through a three-necked flask containing 100 liters of 2-butyr to 3 liters for 3 minutes. Increase the temperature to 80 while stirring. The above monomer solution was added by dropwise addition at a rate of 1 ml / 5 minutes, and the mixture was polymerized for 5 hours. The reaction solution was cooled to 3 Torr or less and poured into 2,0 g of methanol. The resulting white precipitate was collected via filtration, mixed with 400 g of methanol and washed twice. The white precipitate was transferred and dried at 50 ° C for 1 hour to obtain a resin. This resin has 2-nonyl-2-oxanyl methacrylate: 3-hydroxy-1-adamantyl methacrylate: compound of formula (34) = 45. 2: 25.6:29.2 copolymerization ratio A copolymer having a Mw of 9,800. This resin is referred to as "resin (B-8)". Synthesis Example 1 7 46.17 g of 2-mercapto-2-adamantyl methacrylate, 5.179 g of 3-hydroxy-1-adamantyl methacrylate, and 48.65 g of a compound of the formula (34) were dissolved in 20 0 g of 2-butanone was obtained to obtain a homogeneous solution, followed by the addition of 4·3 g of decyl bis-isovalerate to obtain a monomer solution. Nitrogen gas was bubbled through a 1 liter three-necked flask containing 1 gram of 2-butanone for 30 minutes. Increase the temperature to 8 〇 °C while stirring. By 1 〇 ml / 5 points

C:\2D-C0DE\91-09\91114303.ptd Page 128 1304060 V. INSTRUCTION DESCRIPTION (124) The above monomer solution was added dropwise at a rate of the clock, and the mixture was polymerized for 5 hours. The reaction solution was cooled to 30 ° C or below and poured into 2,0 gram of sterol. The resulting white precipitate was collected via filtration, mixed with 40 g of sterol and washed twice. The white precipitate was filtered and dried at 50 ° C for 1 hour to give a resin. This resin has 2-methyl-2-adamantyl methacrylate: 3-hydroxy-1 -adamantyl methacrylate: compound of formula (3 4 ) = 3 9 · 2 : 5. 4:55.4 The copolymer was copolymerized to have a Mw of 9,400. This resin is referred to as "resin (B - 9 )". Synthesis Example 1 8 47.76 g of 2-ethyl-2-hexadecyl methacrylate and 52.24 g of the compound of the formula (34) were dissolved in 2Q0 g of 2-butanone to obtain a homogeneous solution 'subsequently added 3 · 9 3 grams of azobisisovalerate, and a monomer solution. Nitrogen gas was bubbled through a 1 liter three-necked flask containing 100 grams of 2-butanone for 3 minutes. Increase the temperature to 8 ° °c while mixing the edges. The above monomer solution was added by dropwise addition at a rate of 1 Torr / 5 minutes, and the mixture was polymerized for 5 hours. The reaction solution was cooled to 30 ° C or below and poured into 2,0 g of sterol. The white precipitate produced was collected by filtration, mixed with 400 g of sterol and washed twice. The white precipitate was filtered and dried at 50 ° C for 17 hours to obtain a resin. This resin has a copolymer of 2-ethyl-2-adamantyl methacrylate: a compound of the formula (34) = 39.8:60.2 having a copolymerization ratio of η, 600 Mw.

C:\2D-roDE\91-09\91114303.ptd Page 129 1304060 V. INSTRUCTIONS (125) This resin is referred to as "resin (B-1 〇)". Synthesis Example 1 9 41.95 g of 1-ethylcyclohexyl methacrylate and 58 〇 5 g of the compound of the formula (34) were dissolved in 2 gram of 2-butanone to obtain a homogeneous solution 'subsequently added 4 · 3 7 grams of azobisisovalerate 曱g, and a monomer solution. Nitrogen gas was bubbled through a 1 liter three-necked flask containing 1 gram of 2-butanone for 30 minutes. The temperature was raised to 8 (Tc) while stirring. The above monomer solution was added by dropwise addition at a rate of 10 ml/5 minutes, and the mixture was polymerized for 5 hours. The reaction solution was cooled to 3 〇 °c or less. Pour it into 2,00 g of sterol. The white precipitate produced was collected by filtration, mixed with 400 g of methanol and washed twice. The white precipitate was filtered and taken at 50 Drying at ° C for 17 hours to obtain a resin. This resin has 1-ethylcyclohexyl methacrylate: the compound of the formula (34) = 42·1:57·9 has a copolymerization ratio of ^,400 Copolymer of Mw. This resin is referred to as "resin (B - 1 1 )". Synthesis Example 20 2,200 g of 2-ethyl-2-adamantyl methacrylate, 24.74 g of methyl group 3-hydroxy-1-adamantyl acrylate, and 23.26 g of the compound of formula (34) are dissolved in 200 g of 2-butanone to give a homogeneous solution, followed by the addition of 3 · 8 5 g of azobis isovaleric acid The oxime ester was obtained as a monomer solution. The nitrogen gas was bubbled through a 1 liter three-necked flask containing 100 g of 2-butanone for 30 minutes. The temperature was increased to edge 8 billion ° c. Since 1 through milliliters / 5 min

C:\2D-OODE\91-O9\91114303.ptd Page 130 1304060

V. Description of the Invention (126) The above monomer solution was added dropwise at the rate of the clock, and the mixture was polymerized for 5 hours. The reaction solution was cooled to 30 ° C or below and poured into 2,0 g of sterol. The resulting white precipitate was collected via filtration, mixed with &lt;RTIgt; The white precipitate was filtered and dried at 50 ° C for 17 hours to obtain a resin. This resin has 2-ethyl-2-alkanoyl methacrylate: 3-hydroxy-1-adamantyl methacrylate: compound of formula (34) = 44.4: 25.3: 30.3 has a copolymerization ratio of 8 , 700 Mw copolymer. This resin is referred to as "resin (B-1 2 )".

Synthesis Example 2 1 A three-necked flask was charged with 1.52 g of a decane compound of the formula (3 5 ), 1.57 g of a compound of the formula (36), a methyl triethoxy decane of 15 g, and 15 g of 4-methyl-2-pentanone, and 丨· 31 g of 丨 · 75% of oxalic acid water/glutamine. The mixture was allowed to react at 8 Torr for 6 hours while the side was mixed with water, and then the reaction was terminated by cooling with ice. The reaction mixture was poured into a separatory funnel to remove the aqueous layer. The organic layer was washed with ion-exchanged water until the reaction solution became neutral. The organic layer was evaporated under reduced pressure to give a resin. The M w of the resin is 2,5 0 0

Si(〇C2H5)3

(35)

Ch2 F3c—c—CF: (36) c(ch3)3

1304060

Synthesis Example 2 7 g of di-anthracene-^7 η ^ ^ ^ 弟 一 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰铷 铷 + ΠΓ Γ 克 二 二 氧 圜 圜 solution. The mixture was allowed to mix for 6 hours under the dish. Bunde and Jun add acid to neutralize triethylamine. The reaction solution was dropped into a large amount of water u t ^ 丄, a, water r to condense the resin. The coagulated resin was washed several times with pure water.鈇德将;^日 tl,占”,, silly will filter the tree day and dry under vacuum at 50 °c overnight. The resin 乂~ and ^1~/1111 are 9,2 0 0 And 1.8. The structure in which the resin has a 30-mole percentage of a hydrogen atom of a phenolic hydroxyl group in poly(4-hydroxystyrene) by a third butoxycarbonyl group was measured by 13 (: - Results of analysis). This resin is referred to as "resin (B - 14)". Synthesis Example 2 3 41.15 g of 2-mercapto-2-adamantyl acrylate, 5·19 g of methacrylic acid 3-hydroxy- 1-adamantyl ester, and 5 3. 6 g of the compound of formula (34) are dissolved in 200 g of 2-butanone to give a homogeneous solution, followed by the addition of 4 · 4 g of decyl bis-isovalerate. A monomer solution was obtained. The nitrogen gas was bubbled through a 1 liter three-necked flask containing 1 gram of 2-butanone for 3 minutes, and the temperature was raised to 80 ° C while stirring. The rate was passed in milliliters / 5 minutes. Add the above monomer solution by dropwise addition, and make the mixture ♦ a 5 hours. Allow the reaction solution to cool to 30 ° C or below, and pour it into

C:\2D-O0DE\91-09\91114303.ptd Page 132 1304060 V. INSTRUCTIONS (128) 2,0 0 gram of sterol. The white precipitate produced was collected by filtration, mixed with 400 g of sterol and washed twice. The white precipitate was filtered and dried at 50 ° C for 1 hour to give a resin. This resin has 2-methyl-2-adamantyl methacrylate: mercapto-acrylic acid 3-carbyl-1-adamantate: compound of formula (34) = 35.8: copolymerization ratio of 5.1:59.1 It has a copolymer of 9,800. This resin is referred to as "resin (B-15)". Radiation-sensitive resin composition Examples 1 - 19 and Comparative Example 1 The components shown in Table 1 were mixed to prepare a homogeneous solution. The solution was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a composition solution. The solution composition was spin coated onto a tantalum wafer. Then, P B ' was carried out under the conditions shown in Table 2 to form a photoresist coating layer having the thickness shown in Table 2. Regarding the radiation source in the embodiment: a stepper NSR 220 5 EX 12B (numerical aperture: 0.55) manufactured by Nikon c〇rporation was used as a KrF excimer laser (indicated as "KrF" in Table 2) An ArF excimer laser exposure apparatus (numerical aperture: 0.55) manufactured by Nik〇n Corporation was used as an ArF excimer laser (indicated as "ArF" in Table j); manufactured by Ultratech Stepper, lnc. &amp; Excimer laser exposure equipment = X_LS (numerical aperture: 0.60) is used as a 匕 excimer laser (hh in the table), ML "Α1, Ud. Manufactured by direct-write electron beam lithography machine HL-70 0 (The device in which the accelerating voltage is modified to a range of 3 〇仟 electron volts to 5 〇仟 electron volts) is used as an electron beam.

1304060 V. Description of invention (129)

After the conditions were exposed, p e B was subjected to a paddle method using a 2.38 weight percent gas oxidized tetra-ammonium aqueous solution to develop the photoresist pattern at 23 ° C for 1 minute. The photoresist coating is washed with pure water and dried to form a photoresist pattern. The evaluation results of the respective photoresists are shown in Table 3. ^ fExample 2 0 - Μ The ingredients shown in Table 4 were mixed to prepare a homogeneous solution. The solution was passed through a membrane filter having a pore diameter of 0.2 μm to obtain a composition solution. The solution composition was spin coated onto a tantalum wafer. Then, under the conditions shown in Table 5, ruthenium was formed to form a photoresist layer having the thickness shown in Table 5. Soil The photoresist coating was exposed to a KrF excimer laser using a slit NSR2205 EX12B (manufactured by Nikon Corp., numerical aperture: 〇 · 5 5 ), and baked under the conditions shown in Table 5 (PEB). The photoresist pattern was developed by a paddle method using a 2.38 weight percent aqueous solution of tetramethylammonium hydroxide. The photoresist coating is then rinsed with pure water and dried to form a photoresist pattern. The evaluation results of the respective photoresists are shown in Table 6. The evaluation of the photoresists of Examples 1 - 2 and Comparative Example i was carried out as follows. Sensitivity: A sensitivity is evaluated based on the optimum exposure dose. When the photoresist coating formed on the enamel wafer substrate is exposed to light, the PEB and alkali are immediately ordered. For development, washing with water, and drying, it can form a 〇·22 micron line width }:} line and space pattern (1L1S) agent

Page 134 1304060 V. INSTRUCTIONS (130) Quantities. In the embodiment in which an ArF excimer laser is used, an optimum dose which can form a line and space pattern (1L1S) having a line width of 1:1 is used. Resolution: The minimum line and space (丨L丨s) size resolved by the optimal exposure dose is used as the resolution. Mask pattern correlation 1 When using the optimal dose exposure, the 〇· 2 2 micron 〇L 〇S pattern (〇· 2 2 micro = line / 2. 2 micron space) is provided with a design line width of 7 The photoresist coating of the line pattern of 〇% 觅 is indicated as "good", otherwise the photoresist is indicated as "poor". When using the ArF exposure at the optimum dose, when using the optimal dose exposure, the pattern of 〇.16 μm 1Li〇s (0 · 16 6 lines y / 〗 G ^ turn \ 1 Λ. / Heart 1) 6 never provided two lines with a line width of more than 70% of the line width of the design line. The first resist coating indication of the pattern is "good", otherwise the photoresist coating indication It is "poor". The reticle pattern is straightened" will be used when the optimal dose 睬#士(0 9 9 ^ φ ^ The first day can be produced in 0·22 micron 1L5S pattern UJ · with microsurgery lines / 1 η料止', Feng, &gt The difference between the line width of the Ρ3 and the design width (〇. 22 micro-) is the extension of the case. The composition of each component of the composition. The evaluation results are shown in Example 2 4 - 3 4 and compared under the f浐. The evaluation of the photoresist of Example 2 is carried out as the radiation transmittance:

1304060 V. INSTRUCTION DESCRIPTION (131) The composition solution was applied to a quartz plate by spin coating, and baked on a hot plate for 130 seconds: followed by baking for 60 seconds to obtain a photoresist coating having a thickness of 〇·34 μm. The photoresist coating = radiation transmittance was calculated from the absorbance at a wavelength of 93 nm and used as a transparency &quot; standard in the deep uv ray region. Further sensitivity: The composition solution was applied by spin coating to a tantalum wafer (ARC25) (manufactured by Brewer Science Corp.) coated with an ARC25 film having a thickness of 82 angstroms, and was shown in Table 8 on a hot plate. Post-baking was carried out under conditions to obtain a photoresist coating having a thickness of 〇·34 μm. The coating was exposed to radiation through a reticle pattern using an ArF excimer laser exposure device (manufactured by Nikon Corp., lens numerical aperture: 〇·55). After the ρΕβ was carried out under the conditions shown in Table 8, the photoresist coating was developed in an aqueous solution of 2.88% by weight of tetraammonium hydroxide at 25 ° C for 80 seconds, washed with water, and dried to form. Positive photoresist pattern. The optimum dose of a 6 μm line and space pattern (1 L1 S ) having a line width of 1:1 is formed as the sensitivity. Resolution: The minimum line and space (丨L1 s) size resolved by the optimal exposure dose is used as the resolution. Pattern side: The size of the lower side Lb and the upper side La of the rectangular section having a line width of 0·16 μm and a space map f (1L1S) were measured using a scanning electron microscope. The pattern shape of the pattern "〇· 85 &lt;:= U/Lb &lt; = 1" and straight without extension edge is evaluated as "good. 1304060

1304060 V. INSTRUCTIONS OF THE INVENTION (133) a-4 : 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene of nonafluoro-n-butanesulfonic acid] can be dissolved in the form of C-1: 4-hydroxyl Styrene/styrene copolymer (copolymerization ratio: 78:22, Mw-3,100, Mw/Mn=1.13; VPS3020 (manufactured by Nippon Soda Co., Ltd.) &lt;0) Acid diffusion controlling agent D-1 Octyl D-2 -* Ethanolamine D-3 2-Phenylbenzopyrene D-4 2,6 -Dimethylaminoindole D-5 N - Second Butoxycarbonyl-2-Phenylbenzo Imidazole crosslinker E-1 : :N, N, N, N-tetrakis(曱oxymethyl)acetylene urea other additives

F-l: tert-butyl deoxycholate F - 2 · deoxycholic acid tert-butoxycarbonyl methyl ester F - 3 : lithocholic acid third butoxycarbonyl hydrazine solvent

G - 1 : ethyl lactate G-2 : ethyl 3-ethoxypropionate G - 3 : propylene glycol monoterpene ether acetate G-4 : 2-heptanone G-5 : cyclohexanone G - 6 : τ One

C:\2D-CODE\91-09\91114303.ptd Page 138 1304060 V. INSTRUCTIONS (134) Units in parentheses: parts by weight

Acid generator resin acid diffusion control agent crosslinker other additive solvent example] Al(3) Bl(lOO) D-3(0.1) - - Gl(800) Example 2 Α-2(3) Bl(100) D-2(0.1) - - Gl(800) Example 3 Α-3(3) B-1(1 00) D-4(0.3) - - G -1(800) Example 4 Α-4(3) ) Bl(lOO) D-3(0.1) - - G-1(800) Example 5 A-3(l) a-1(6) B-1(100) D-5(0.2) - - G- 1(400) G-3(400) Example 6 Α-3(2) B-2(100) D-2(0.1) - - G-1(400) G-2(400) Example 7 A- 3(7) B-3(100) D-3(0.1) - - G-1(400) G -3(400) Example 8 A-2(2) B-4(100) D-1(0.1) - - G-1(400) G-3(400) Example 9 A-1(2) B-5(90) D-3(0.1) - Fl(10) G-4(700) G-5(300) Example 10 A-1(5) B-6(92) D-3(0.4) - F-2(8) G-3(700) G-6(50) Example η A-2(2) B -13(100) D-3(0.1) - - G-3(1200) Example 12 A-2(3) Bl(100) D-3(0.1) - - Gl(800) Example 13 A-2 (3) Cl(97) B-4(3) Dl(Ol) El(7) - Gl(550) G-2(250) Example 14 A-1(4) A-2(l) B-7 (90) B-ll(10) D-3(0.4) - G-4(250) G-6(550) Example 15 A· 1(4) A-5(l) B-7(90) B -ll(10) D-3(0.3) - Reference G-4(250) G~6(550) Example 16 A-1(5) B -8(60) B-10(40) D-3(0.4) - - G-4(800) Example Port A-1(5) B-9(100) D-3(0.4) - - G- 4(800) Example 18 A-1(4) A-2(l) B -12(100) D-3(0.4) - - G-4(800) Example 19 A-1(4) A- 5(l) B-12( 100) D-3(0.3) - - 0-4(800) Comparative Example 1 a-1(3) B-1(100) D-3(0.1) - - G- 1(400) G-3(400) Page 139 C:\2D-CODE\91-09\91 1 14303.ptd 1304060 V. INSTRUCTIONS (135) TABLE 2 Thickness 辐射 Radiation PEB (in) Temperature Time Temperature Time (°C) (seconds) (°C) (seconds) Example 1 5 000 000 120 90 KrF excimer laser 130 90 Example 2 5,000 120 90 KrF excimer laser 130 90 Example 3 5,000 120 90 KrF Molecular Laser 130 90 Example 4 5,000 120 90 KrF Excimer Laser 130 90 Example 5 5,000 120 90 KrF Excimer Laser 130 90 Example 6 5,000 140 90 KrF Excimer Laser 140 90 Example 7 5,000 130 90 KrF excimer laser 130 90 Example 8 5,000 100 90 KrF excimer laser 100 90 Example 9 3,000 140 90 ArF excimer laser 140 90 Example 10 353〇〇130 90 ArF excimer laser 130 90 Example η 15000 130 90 F2 Laser 110 90 Example 12 3,000 120 90 Electron beam 130 90 Example 13 5,000 90 60 KrF excimer laser 110 90 Example 14 3,300 130 90 ArF excimer laser 130 90 Real 1^ Example 15 353〇〇130 90 ArF Excimer Laser 130 90 Λ Example 16 353〇〇130 90 AtF Excimer Laser 110 90 Example 17 3,300 130 90 ArF Excimer Laser 130 90 Real &amp; Example] 8 3,300 130 90 ArF Excimer Thunder Shot 110 90 Example 1.9 3,300 130 90 ArF excimer laser 110 90 than $ pay implementation 5,000 120 90 KrF excimer laser 130 90 cases 1.

C:\2D-CODE\91-09\91114303.ptd Page 140 1304060 V. INSTRUCTIONS (136) Table 3 Resolution Sensitivity Mask Pattern Correlation Example 1 0.2] μι in 3 60 J/m2 Good implementation Example 2 0.2 1 μ m 3 20 J/m 2 Good Example 3 0.2 0 μ in 3 00 J/m 2 Good Example 4 0.2 0 μ m 3 50 J/m 2 Good Example 5 0.2 0 μ m 3 20 J/m 2 Good implementation swallowing []6 0.2 1 μ m 3 90 J/m2 good example 7 0.21 μ m 3 60 J/m2 good example 8 0.2 0 μ m 380 J/m2 good example 9 0.1 7 μ m 8 00 J /m2 Good example 10 0.1 5 μ m 3 00 J/m 2 Good example η 0.1 7 μ m 2 00 J/m 2 Good example 〗 2 0.1 6 μ m 4 μ Ο Good example 13 0.2 0 μ m 2 60 J/ M2 good example 14 0.1 5 μ in 260 J/m2 good. Example 15 0.1 5 μ m 2 80 J/m 2 good example 〖6 0.1 5 μ ιίί 3 20 J/m2 good example 17 0.1 5 μ m 2 80 J/m2 watts good example 18 0.1 5 μ m 240 J/m2 good example 〗 9 0 . 1 5 μm 270 J/m2 good comparative example 1 0.2 ] μ m 3 20 J/m2 Z] two

IIH1I C:\2D-OODE\91-O9\91114303.ptd Page 141 1304060 V. INSTRUCTIONS (137) Table 4 Acid generator resin acid diffusion control agent Solvent Example 20 A-6(2) a-]( 6) Bl(lOO) D'V(0.2) G,](400) G - 3(400) Example 21 A-6(2) al(6) B-2(l00) D-3(0.2) Gl (400) G, 3 (400) Example 22 A-6(2) al(6) B-14(100) D-3(0.2) Gl(400) G-3(400) Example 23 A-6 (2) a-3(6) B-4(100) D-2(0.2) Gl(400) G-3(400) Table 5 Thickness PB Radiation PEB (A) Temperature Time Temperature Time (°C) (seconds) (°C) (seconds) Example 20 5,000 120 90 KrF excimer laser 130 90 Example 21 5,000 120 90 KrF excimer laser 130 90 Example 22 5,000 90 90 KtF excimer laser 100 90 Example 23 5,000 100 90 KrF excimer laser 100 90 _ 11 C:\2D-CODE\91-09\91114303.ptd Page 142 1304060 V. Invention description (138) Table 6 Resolution sensitivity reticle pattern fidelity embodiment 20 0.1 8 μ m 3 10 J/m2 10 Example 21 0.2 0 μ m 3 30 J/m 2 1 2 Example 22 0.2 0 μ m 290 J/m 2 8 Example 23 0.1 8 μ in 3 00 J/m 2 4

C:\2D-CODE\91-09\91114303.ptd Page 143 1304060 V. Inventive Note (139) Table 7 Units in parentheses: parts by weight acid generator shed acid diffusion control agent other additive solvent Example 24 A-8(5) B-8(92) D-3(0.10) F-2(8) G-3(700) Example 25 A-8(5) B-8(92) D-3(0.10 F-2(8) G-3(700) Example 26 A-2(5) B-8(92) D-3(0.30) F-3(8) G-3(700) Example 27 Al (5) B-8(92) D-3(0.30) F-3(8) G-3(700) Example 28 Al(5) B-8(92) D-3(0.30) F-2( 8) G-3 (700) Example 29 A-7 (5) B-8 (92) D-3 (0.15) F-2 (8) G-3 (700) Example 30 A-4 (5) B-8(92) D-3(0.10) F-2(8) G-3(700) Example 31 Al(5.5) B-7(65.8) B-15(28.2) D-5(0.43) F&gt ; 2(6) G-4(500) G-5(200) Example 32 Al(5.5) B-7(65.8) Bl 5(28.2) D-5(0.43) F-2(6) G-4 (500) G-5 (200) Example 33 Α·1(5.5) B-7(28.2) B-15(65.8) D-5(0.43) F-2(6) G-3(470) G-4(200 G-5(30) Example 34 Al(5.5) B-7(28.2) B-15(65.8) D-5(0.43) F-2(6) G-3(470) G_4(200) G- 5(30) Comparative Example 2 a-4(5) B-8(92) D-3(0.30) F-2 (8) G-3(700)

Painting·· C:\2D-OODE\91-O9\91114303.ptd Page 144 1304060 photoresist coating thickness substrate PB PEB (//m) temperature time temperature time (°C) (sec) (°C (sec) Example 24 0.34 ARC25 130 90 130 90 Example 25 0.34 ARC25 130 90 130 90 Example 26 0.34 ARC25 130 90 130 90 Example 27 0.34 ARC25 130 90 130 90 Example 28 0.34 ARC25 130 90 130 90 Implementation Example 29 0.34 ARC25 130 90 130 90 Example 30 0.34 ARC25 130 90 130 90 Example 31 0.34 ARC25 130 90 130 90 Example 32 0.34 ARC25 130 90 130 90 Example 33 0.34 ARC25 130 90 130 90 Example 34 0.34 ARC25 130 90 130 90 Comparative Example 2 0.34 ARC25 130 90 130 90 Radiation Transmittance (%) Sensitivity (J/m2) Resolution (#m) Pattern Shape Development Exposure Apparatus 瑕疵 Inspection Apparatus Example 24 71 238 0.13 Good 0 S203B KLA2115 Example 25 71 238 0.13 Good 0 S306C KLA2351 Example 26 69 232 0.13 Good 12 S203B KLA2115 Example 27 70 229 0.13 Good 0 S203B KLA2115 Example 28 70 229 0.13 Good 0 S306C KLA2351 Example 29 72 249 0.13 Good 4 S203B KLA2115 Example 30 70 283 0.13 Good 1 S203B KLA2115 Example 31 71 252 0.13 Good 0 S203B KLA2115 Example 32 71 252 0.13 Good 0 S306C KLA2351 Example 33 70 254 0.13 Good 0 S203B KLA2115 Example 34 70 254 0.13 Good 0 S306C KLA2351 Comparative Example 2 70 224 0.13 Good 526 S203B KLA2115 V. Invention Description (140) Table 8 Table 9 ΙΙΙΒϋΙΙ

C:\2D-C0DE\91-09\91114303.ptd Page 145 1304060 V. INSTRUCTION DESCRIPTION (141) The acid generator (I) of the present invention exhibits a relatively high flammability and no bioaccumulation, and produces a high acidity. And high boiling acid. The acid generator exhibits high transparency to deep ultraviolet light such as KrF excimer laser, ArF excimer laser, F2 excimer laser, or EUV, and electron beam, and produces a photoacid generator as a reaction to the above radiation. Or as a heat-sensitive acid generator for heat reaction (I - a). In particular, the acid generator can be suitably used as a photoacid generator in a radiation-sensitive resin composition for chemically amplifying a photoresist. The sulfonic acid (I - a) of the present invention is useful as a component for forming an antireflection film on the upper layer or the lower layer provided in the process of forming a photoresist pattern. The sulfonate (1C) and the sulfonium halide compound (4A) of the present invention are useful as a reaction intermediate material for synthesizing the acid generator (I). Further, a sulfonic acid (丨_a), a sulfonate (1 C ), and a sulfonium halide compound (4 A ) are useful as a raw material for synthesizing a sulfonic acid derivative. The radiation-sensitive resin composition of the present invention containing an acid generator (I) is a deep ultraviolet light such as a KrF excimer laser, a human excimer laser, a 1?2 quasi-knife laser, or an EUV, and an electron Beam reaction, which is highly sensitive to radiation, has a moderately short diffusion length in the photoresist coating, exhibits excellent resolution], low correlation of mask pattern density, and can be suitably used in anticipation Increasingly, it is in the field of microfabrication represented by the manufacture of integrated circuits. It is apparent that various modifications and changes can be made in the present invention in light of the above teachings. Therefore, it is to be understood that the invention may be practiced otherwise than as specifically described herein.

Page 146

1304060 Brief Description of the Drawing Figure 1 shows the results of 1 Η-NMR analysis of the acid generator (A-1). Figure 2 shows the results of mass analysis of the cationic group of the acid generator (A-1). Figure 3 shows the results of mass analysis of the anion group of the acid generator (A-1). Figure 4 shows the results of 1 Η - N M R analysis of the acid generator (A - 2 ). Figure 5 shows the results of mass analysis of the cationic groups of the acid generator (A-2). Fig. 6 shows the results of mass analysis of an anionic group of the acid generator (A-2). Fig. 7 shows the results of 1 Η-NMR analysis of the acid generator (A-3). Fig. 8 shows the results of mass analysis of the cationic group of the acid generator (A-3). Figure 9 shows the results of mass analysis of the anion group of the acid generator (A-3). Fig. 10 shows the results of 1 H-NMR analysis of the acid generator (A-4). Figure 11 shows the results of 1 H-NMR analysis of the acid generator (A-5). Fig. 1 2 shows the results of mass analysis of the cationic groups of the acid generator (A-5). Fig. 13 shows the results of mass analysis of the anion group of the acid generator (A-5). Fig. 14 shows the results of mass analysis of the cationic groups of the acid generator (A-6). Figure 15 shows the mass analysis result of the anion group of the acid generator (A-6).

C:\2D-C0DE\91-09\91114303.ptd第147页

Claims (1)

JUL 0 2 2008 Replacement 1304060 VI. Scope of Application I An acid generator having the structure of the following chemical formula (Ι-A) or (I-B), Wherein Z1 and Z2 represent a fluorine atom or a linear or branched perfluoroalkyl group having 碳_丨〇 a carbon atom, and Y1 represents a single bond, -〇-, __s-, carbonyl, sulfinylene, basket, Amidino, 1,; [-extended ethyl, U-extended ethyl, propyl, 1-mercaptopropyl, 1-ethylpropionyl, trimethylene, difluoromethylene, tetrafluoro- 1,2-extended ethyl, 1,2-phenylene, [,3-phenylene, or 1,4-phenylene, R' represents keto (=〇), hydroxyl, carboxyl, formazan a straight or branched alkyl group having 1 to 10 carbon atoms, a straight or branched chain vinylidene group having one carbon atom, a monovalent cyclic organic group having 1 to 12 carbon atoms, having 6-20 An aryl group of a carbon atom, a linear or branched chain oxy group having 1 carbon atom, an aryloxy group having 6 to 20 carbon atoms, a linear or branched alkanecarbonyl group having 2 to 10 carbon atoms, An arylcarbonyl group having 7 to 20 carbon atoms, a linear or branched alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, k being an integer of 0 or more, and η Is an integer of 〇-5. II II 1 1 II 91114303 (replacement) - 2.ptc Page 148 1304060 Case No. 91 Π 43 s. Patent application scope 曰 曰 ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ ΐ : : : : ΐ : : : : Ζ1 - Y1—c—S03- M+ (1-A) 1-C-S03- M+ (lB) η !: 丨 二 1 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表Gas-burning group, γι retained retention 1 ^ ^ represents early bond, -0-, -S-, carbonyl, sub-continuation ί:; base, ethyl, ethylene, propyl, methyl propyl, I-ethyl propyl, trimethylene, diyl, tetrafluoro-1,2-extended ethyl, anthracene, 2-phenylene, anthracene, 3-phenylene, or 1,4-extension base, R a keto group (=〇), a hydroxyl group, a carboxyl group, a carbhydryl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched chain vinylidene group having 1 carbon atom, Divalent monocyclic organic group of 2 carbon atoms, aryl group of 6-20 carbon atoms, linear or branched alkoxy group having 1 carbon atom, 6-20 broken atoms An oxy group, a linear or branched chain carbonyl group having 2 to 1 carbon atoms, An aryl-Wiki group having 7 to 20 carbon atoms, a linear or branched alkoxycarbonyl group having 10 carbon atoms, an aryloxycarbonyl group having 7 to 2 carbon atoms, k being an integer of 0 or more, η An integer of 0-5, and M+ is 91114303 (replacement)-2.ptc page 149 3: An acid generator according to claim 2, wherein M+ is a cation represented by the following chemical formula (i), R2—R 3 (i) /, wherein R, R and 1^3 represent substituted or unsubstituted, straight or branched alkyl groups having from 1 to 1 carbon atoms, respectively, having from 6 to 18 carbons The atom is substituted with an unsubstituted aryl group, or two or more of the group, R2, and R3 together with a sulfur atom in the chemical formula form a ring. The acid eliminator as described in claim 2, wherein m+ is a ruthenium cation of the following formula (11), (ϋ) R4 — 1+ — R5 wherein R 4 and R 5 each represent a substituted carbon with HO or Unsubstituted, linear or branched alkyl groups, and 6 5 - succinic acid, iodine atoms of the 1G sub-form form together form a ring. 5. The species t produces hydrazine, which is the following chemical formula (2-A) or (2-# 醯 醯 醯 醯 化合物 化合物 , N 150 150 150 150 150 150 150 150 150 150 150 150 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 130 (2 -A) (2-B) ; lZ and Z represent a fluorine atom or a linear or branched chain of 10 carbon atoms, and Yi represents a single bond, —〇—, —s— , carbonyl, sulfoxime, beryllyl, methylene, 1, 1: 1-ethyl, 1,2-extended ethyl, propyl 1-methylpropyl, ethyl ethyl propyl, Trimethylenemethyl, tetrafluoro-, 1,2-extended ethyl, anthracene, 2-phenylene, 1,3-phenylene, or 1,4-extension, R' represents _ group (=〇 a hydroxyl group, a carboxyl group, a fluorenyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a straight or branched chain vinylidene group having 丨-iO carbon atoms, having 12 carbon atoms Monovalent ring organic group, aryl group having 6-20 carbon atoms, linear or branched chain decyloxy group having 10 carbon atoms, aryloxy group having 6-20 carbon atoms, 2-1〇 a linear or branched alkanecarbonyl group of one carbon atom, an aromatic carbonyl group having 7 to 20 carbon atoms, a linear or branched alkoxycarbonyl group having 10 carbon atoms, and an aryloxy group having 7 to 2 carbon atoms a carbonyl group, k is an integer of 0 or more, η is an integer of 0-5, and r6 and R7 each represent a hydrogen atom or The substituted or unsubstituted monovalent organic group, or 91114303 (replace)-2.Ptc第151页 ο (2-6) 6 - a positive type radiation-sensitive resin composition comprising: (A) an acid generator of the first application scope of the patent, and (B) a base containing an acid cleavable group or a base which is lowly soluble Resin, when the acid cleavable group dissociates, the resin becomes soluble in alkali. A positive radiation-sensitive resin composition comprising: (A) an acid generator according to item 1 of the patent application, (C) an alkali-soluble resin, and (D) an alkali-soluble angle control agent. 91114303 (replacement)-2.Ptc Page 152 1304060 Case No. 91914303 Revision of the year 6. Patent application scope 8. A negative-type radiation-sensitive resin composition, including: (A) Acid production in the first application of the patent scope The agent (C) is a soluble resin, and (E) a compound which can crosslink the alkali-soluble resin in the presence of an acid. 91114303 (replace)-2.ptc第153页