TW200830046A - Negative resist composition for an electron beam and resist pattern formation method - Google Patents

Abstract

A negative type resist composition for an electron beam comprising at least one member selected from the group consisting of the hydrolysate of alkoxysilane-compound represented by the following general formula (I) and the condensate of alkoxysilane-compound represented by the following general formula (I), and a nonionic acid generator component (B): wherein, R1 represents a hydrogen atom or a 1-valent organic group; R2 is 1-valent organic group; n is an integer of 1 to 3.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative resist composition for an electron beam and a method for forming a photoresist pattern. The present application claims priority based on Japanese Patent Application No. 2 006-2 60805 filed on Sep. 26, 2006, the disclosure of which is incorporated herein. [Prior Art] In the lithography technique, for example, a photoresist film obtained from a photoresist material is formed on a substrate, and for the photoresist film, a photomask of a specific pattern is formed by radiation such as light or electron lines. The selective exposure is carried out by applying a development process to form the photoresist film into a photoresist pattern having a specific shape. The portion of the exposure which is changed to have a characteristic of being dissolved in the developer is referred to as a positive type, and the portion of the photoresist which is exposed to have a property of not being dissolved in the developer is referred to as a negative type. In recent years, in the manufacture of semiconductor elements or liquid crystal display elements, with the advancement of the lithography technique, the pattern has been rapidly refined. The method of miniaturization is generally carried out in such a manner as to shorten the wavelength of the exposure light source. Specifically, ultraviolet rays which are represented by g-line and i-line are conventionally used. However, KrF excimer lasers or ArF excimer lasers are now being used for mass production of semiconductor components. Further, F2 excimer lasers, electron beams, EUV (extreme ultraviolet rays) or X-rays having shorter wavelengths for the aforementioned excimer lasers have also been started. In the case of a photoresist material, it is sought to have sensitivity to the aforementioned exposure light source, and has a lithographic characterization characteristic such as resolution of a reproducible fine-size pattern. The photoresist material which satisfies the above requirements is generally used to contain a base resin which changes the alkali solubility based on the action of an acid, and an enhanced chemical type resist which generates an acid generator by exposure to an acid. For example, a positive type enhanced chemical type photoresist, which is a resin containing an acid-based action as a base resin to increase alkali solubility, and an acid generator component which is formed by exposure to an acid when formed in a photoresist pattern The agent generates an acid and causes the exposed portion to form an alkali solubility. Further, a negative-type enhanced chemical type photoresist, for example, a resin component having a carboxyl group, a crosslinking agent having an alcoholic hydroxyl group, and an acid generator, and an acid generated by the acid generator when the photoresist pattern is formed The action is such that the carboxyl group of the resin component reacts with the alcoholic hydroxyl group of the crosslinking agent, and the resin component changes from alkali solubility to insolubility. At present, the base resin of the photoresist used in the ArF excimer laser lithography etching has excellent transparency in the vicinity of 193 nm. Generally, the main chain is derived from (meth) acrylate. A resin (acrylic resin) constituting the unit (for example, refer to Patent Document 1). [Patent Document 1] JP-A-2003-24 1 3 85 SUMMARY OF THE INVENTION Therefore, in the future, a novel photoresist material capable of providing various kinds of lithography etching characteristics such as high resolution is sought. -5- 200830046 In particular, with the recent gradual miniaturization of the pattern, it is urgent to seek a photoresist material having a good sensitivity to an electron beam having a wavelength shorter than that of the excimer laser. The present invention has been made in view of the above circumstances, and has been proposed to provide a novel negative-type photoresist composition for an electron beam and a method for forming a photoresist pattern using the negative-type photoresist composition for an electron beam. In order to achieve the above object, the present invention adopts the following constitutional contents. That is, the first aspect of the present invention is a negative-type photoresist composition for an electron beam, which is characterized by containing a hydrolyzate of an alkoxydecane compound represented by the following formula (I). At least one compound (A) selected from the group consisting of condensates of the alkoxydecane compound represented by the following formula (I), and a nonionic acid generator (B), R1 -Si(OR2)4-n [In the formula (I), R1 is a hydrogen atom or a monovalent organic group, R2 is a monovalent organic group, and η is an integer of 1 to 3]. Further, a second aspect of the present invention is a method for forming a photoresist pattern, comprising: using a negative photoresist composition for an electron beam of the first aspect; a step of forming a photoresist film on the substrate, a step of exposing the photoresist film, and a step of developing the photoresist film to form a photoresist pattern. In the scope of the present specification and the patent application, "organic group" means a group containing a carbonogen-6 - 200830046 "which may also have an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom). (A fluorine atom, a chlorine atom, etc.), etc. In the present specification, the "alkyl group" is a monovalent saturated hydrocarbon group containing a linear, branched or cyclic group, unless otherwise specified. The "lower alkyl group" means an alkyl group having 1 to 5 carbon atoms. "Exposure", unless otherwise specified, means the meaning of electron beam irradiation. The present invention can provide a novel negative-type photoresist composition for an electron beam and a method for forming a photoresist pattern using the negative-type photoresist composition for an electron beam, a negative-type photoresist composition for an electron beam. The negative-type photoresist composition for an electron beam is a condensate containing a hydrolyzate of the alkoxydecane compound represented by the above formula (I) and an alkoxydecane compound represented by the following formula (I). At least one compound (A) (hereinafter referred to as (A) component) and a nonionic acid generator (B) (hereinafter referred to as component (B)) selected from the group formed. <(A) Component> In the present invention, the component (A) is a hydrolyzate and/or a condensate of the alkoxydecane compound represented by the above formula (I). The alkoxydecane compound represented by the above formula (I) is hydrolyzed to form a hydroxyl group or an alcohol by hydrolysis. Subsequently, two molecules of the aforementioned alcohol are condensed to form a network of Si-0-Si to obtain a component (A). 200830046 In the above formula (I), R1 is a hydrogen atom or a monovalent organic group, and R2 is a monovalent organic group. In R1 and R2, a monovalent organic group such as an alkyl group, an aryl group, an allyl group or a glycidyl group. Among them, an alkyl group and an aryl group are preferred. The alkyl group and the aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include a fluorine atom, a linear chain having 1 to 6 carbon atoms, a branched or cyclic alkyl group, and the like. In the present specification, "may have a substituent" means that a part or the whole of a hydrogen atom such as an alkyl group or an aryl group is substituted with a substituent. The alkyl group is preferably a carbon number of 1 to 5 (lower alkyl group), for example, a methyl group, an ethyl group, a propyl group, a butyl group or the like. Further, the alkyl group may be in the form of a linear chain or a branched chain, and as described above, for example, a hydrogen atom may be substituted by a fluorine atom or the like. The aryl group is preferably a carbon number of 6 to 20, for example, a phenyl group, a naphthyl group or the like. In the above formula (I), n is an integer of from 1 to 3. Specific examples of the alkoxydecane compound represented by the above formula (I) include the following compounds. (i) In the case of n = 1, a trialkoxy decane compound such as a trimethoxy decane compound, a triethoxy decane compound or a tripropoxy decane compound (in the case where R1 is a hydrogen atom) = monomethyltrimethoxy decane compound , monomethyl triethoxy decane compound, monomethyl tripropoxy decane compound, monoethyl trimethoxy decane compound, monoethyl triethoxy decane compound, monoethyl tripropoxy decane compound, monopropyl a monoalkyltrialkoxydecane compound of a trimethoxyoxane compound, a monopropyltriethoxydecane compound, etc. -8-200830046; a monophenyl group such as a monophenyltrimethoxydecane compound or a monophenyltriethoxydecane compound; A trialkoxy decane compound or the like. (ii) In the case of n=2, one of the dimethoxy decane compound, the diethoxy decane compound, the dipropoxy group, the hydrazine hydride compound, and the like a gas atom); dimethyl dimethoxy decane compound, dimethyl diethoxy decane compound, dimethyl dipropoxy decane compound, diethyl dimethoxy decane compound, diethyl diethoxy a dialkyldialkoxy group such as a decane compound, a diethyldipropoxydecane compound, a dipropyldimethoxydecane compound, a dipropyldiethoxydecane compound, or a dipropyldipropoxydecane compound a decane compound; a diphenyl dimethoxy decane compound, a diphenyl diethoxy decyl compound, or the like; a diphenyl bis oxene compound; and (iii) a methoxy decane compound, Ethoxy decane compound, propoxylated compound compound, etc. (in the case of R as an ammonia atom); trimethyl methoxy decane compound, trimethyl ethoxy decane compound, trimethyl propylene oxide Base decane compound, triethyl methoxy decane compound, triethyl a trialkylalkoxydecane compound such as an ethoxysilane compound, a triethylpropoxydecane compound, a tripropylmethoxydecane compound or a tripropylethoxysilane compound; a triphenylmethoxydecane compound, triphenyl a triphenyl alkoxy decane compound such as an ethoxysilane compound, etc. -9- 200830046 In the above, a trialkoxy decane compound such as a trimethoxy decane compound, a triethoxy decane compound or a tripropoxy decane compound is used. (wherein R1 is a hydrogen atom); a monomethyltrialkoxide compound such as a monomethyltrimethoxydecane compound, a monomethyltriethoxydecane compound or a monomethyltripropoxydecane compound is preferred, More preferably, it is a trialkyloxydecane compound (wherein R1 is a hydrogen atom), and among them, a triethoxyoxane compound is preferable. In the negative-type photoresist composition for an electron beam of the present invention, the above formula (I) The alkoxydecane compound shown may be used singly or in combination of two or more. The negative-type photoresist composition for an electron beam of the present invention contains the above formula (I). Show In the case of the condensate of the alkoxydecane compound, the mass average molecular weight (Mw) of the condensate (polystyrene equivalent of the gel permeation chromatography method) is preferably 200 to 50,000, and is 500 to 1,000,000. More preferably, it is preferably from 1,000 to 3,000. When it is within this range, the coating property of the negative-type photoresist composition for an electron beam can be improved, and the electron beam can be improved when a condensate is present. The adhesion of the photoresist film (hardened film) formed by the negative photoresist composition to the substrate. The condensate of the compound oxide sand compound of the above formula (I) is an alkane as a polymerization monomer. The oxoxane compound can be obtained by reacting in an organic solvent or an acid catalyst (hereinafter, the condensate solution containing the alkoxydecane compound obtained here is called "the coating liquid for forming a decane-based film" "). As the alkoxydecane compound which is a polymerization monomer, one type of -10-200830046 may be used alone, or two or more types may be combined and condensed. The organic solvent is preferably an alkanediol dialkyl ether, for example, from the viewpoint of improving the storage stability (e.g., the effect of preventing gelation) of the coating liquid for forming a decane-based film. The alkylene glycol dialkyl ether, such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether , diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl Ether, etc. Among them, preferred is a dialkyl ether of propylene glycol, and most preferably propylene glycol dimethyl ether. These organic solvents may be used singly or in combination of two or more kinds. The amount used is a ratio of 10 to 30 moles relative to the alkoxydecane compound 1 mole. The degree of hydrolysis of the alkoxydecane compound as a premise of condensation can be adjusted according to the amount of water to be added. [Generally, it is a total of the compound of the oxidized sand compound shown in the above formula (I). The number of ears 'add 1 to 倍 mole is better, and more preferably 1 · 5 to 8 times the molar ratio. When the amount of addition of water is 1 time or more, the degree of hydrolysis can be increased to further increase the reactivity of the alkoxy decane compound (the above-mentioned alcohol) with each other. When the amount is less than 10 times the molar amount, the gelation is suppressed, and the storage stability of the coating liquid for forming a decane-based film can be improved. Further, the acid catalyst used in the condensation of the oxonyl lanthanum compound represented by the above formula (1) is not particularly limited. It can be used in the conventionally used -11 - 200830046 organic acid, inorganic acid, etc. be usable. An organic acid such as an organic carboxylic acid such as acetic acid, propionic acid or butyric acid. Inorganic acids, for example, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and the like. The acid catalyst may be directly added to the mixture of the alkoxydecane compound and water, or may be added as an acidic aqueous solution while being added to the water in the alkoxydecane compound. The hydrolysis reaction usually ends in about 5 to 100 hours. In addition, in an organic solvent containing one or more kinds of alkoxydecane compounds represented by the above formula (I), an aqueous solution of an acid catalyst is allowed to react in a heating temperature of not more than room temperature of 80 ° C. The reaction can be completed in a shorter reaction time. The hydrolyzed alkoxydecane compound is then subjected to a condensation reaction, and as a result, a component (A) in which a Si-0_si network is formed can be obtained. Further, the component (A) may contain a hydrolyzate of an alkoxydecane compound while containing a condensate of an alkoxydecane compound. In the production of the negative-type resist composition for an electron beam of the present invention, the component (A) is preferably used in the form of the above-described coating liquid for forming a decane-based film. In the coating liquid for forming a decane-based film, for example, a solution obtained by hydrolyzing and condensing the alkoxydecane compound represented by the above formula (I) may be concentrated or an organic solvent (preferably the above alkane two) may be used. Alcohol dialkyl ether, etc.) is diluted to the desired solid concentration. The solid component concentration can be measured, for example, by a weight drying method. In the weight drying method, for example, the mass (W 1 ) of the coating liquid for forming a decane-based film after the separation is measured, and dried at 500 ° C for 1 hour, and then the quality after drying is determined from -12 to 200830046 ( W2) 'Method of calculating the concentration of solid components according to the following mathematical formula. Mathematical formula: solid content concentration (% by mass) = W2 / Wlxl00 The concentration of the coating liquid for forming a decane-based film can be approximated by the concentration of SiO 2 in the component (A). The concentration of the SiO 2 conversion can be determined from the structure of the component (A) based on the solid component concentration (% by mass) calculated by the above mathematical formula. In the present invention, the SiO 2 conversion concentration of the coating liquid for forming a decane-based film can be appropriately adjusted in accordance with the purpose of use, and is usually preferably 2 to 15% by mass, more preferably 5 to 12% by mass. <(B) Component> In the present invention, the component (B) is a nonionic acid generator. The component (B) is a compound which generates an acid by sensing an electron beam. When the component (B) is contained, a photoresist pattern can be obtained by development. The reason for this is that it is caused by the occurrence of acid by irradiation of electron beams and the formation of a network in which (A) components form S i - Ο - S i with each other. Further, when the component (B) is contained, the film stability (PCD · post coating delay) after coating can be improved, and the solution has good solubility. The component (B) has a small change in solubility for the developer (especially the developer) and has stability. -13- 200830046 (B) The composition is not particularly limited, and it can be used as a component which has been proposed as an acid generator for enhancing chemical resistance. The nonionic acid generators 'to date' such as sulfonate acid generators; double-base or bisarylsulfonium diazobenzenes, poly(disulfonyl)diazomethane a diazomethane acid generator such as an oxadiamine acid generator, a bismuth acid generator, a -3-keto oxime acid generator, a diterpene acid generator, a nitrobenzyl sulfonate An acid generator, a sulfonic acid ester acid generator, a sulfonate acid generator of an N-hydroxyindenine compound, an sulfonate acid generator, and the like Know the substance. In the present specification and the patent application, an oxime sulfonate-based acid generator, for example, a compound (B-1) having at least one group represented by the following formula (II), which has an acid generated by electron beam irradiation Characteristics. These sulfonate-based acid generators (B-1) are often used in a reinforced chemical-type resist composition, which can be optionally used. [Chem. 2] -C=N—0—S〇2—R31 R32 (II) [In the formula (II), R31 and R3 2 each independently represent an organic group]. The organic group of R31 may be a linear, branched or cyclic alkyl group or an aryl group. The above alkyl group or aryl group may have a substituent. The substituent is not limited to any, and may be, for example, a fluorine atom, a linear one having a carbon number of 1 to 6, a branched chain or a 200830046 cyclic alkyl group. The alkyl group preferably has a carbon number of from 1 to 20, preferably has a carbon number of from 1 to 10, more preferably has a carbon number of from 1 to 8, and is preferably a carbon number of from 1 to 6, preferably a carbon number of from 1 to 4. . The alkyl group is particularly preferably an alkyl group partially or wholly halogenated (hereinafter also referred to as a halogenated alkyl group). Further, a partially halogenated alkyl group means an alkyl group in which a part of a hydrogen atom is replaced by a halogen atom, and a completely halogenated alkyl group means an alkyl group in which a hydrogen atom is entirely substituted by a halogen atom. A halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably an atom. That is, the halogenated yard base is preferably a fluorinated yard base. The aryl group is preferably a carbon number of 4 to 20, preferably a carbon number of 4 to 10, and more preferably a carbon number of 6 to 10. The aryl group is particularly preferably a partially or fully halogenated aryl group. Further, a partially halogenated aryl group means an aryl group substituted by a halogen atom of a part of a hydrogen atom, and a completely halogenated aryl group means an aryl group obtained by completely replacing a hydrogen atom with a halogen atom. R31 is particularly preferably an alkyl group having 1 to 4 carbon atoms which has no substituent, or a fluorinated alkyl group having 1 to 4 carbon atoms. The organic group of R32 is preferably a linear, branched or cyclic alkyl group, aryl group or cyano group. The alkyl group or the aryl group of R32 is, for example, the same as the alkyl group or the aryl group exemplified in the above R31. R32 is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms which has no substituent, or a fluorinated group having 1 to 8 carbon atoms. The oxime sulfonate-based acid generator (B-1) is more preferably a compound represented by the following formula (B- -15-200830046 2) or (B-3). [Chem. 3] R34—C=N—Ο—S02—R35 R33 · · · (B-2) [In the formula (B-2), R33 is a cyano group, an alkyl group having no substituent or an alkyl halide; R34 is an aryl group; R3 5 is an alkyl group having no substituent or a halogenated alkyl group]. [Chemical 4] • C=N R36 ——Ο——S〇2——R38

· (B-3) [In the formula (B-3), R36 is a cyano group, an alkyl group having no substituent or a halogenated alkyl group; R37 is a 2 or 3 valent aromatic hydrocarbon group; and R38 is a substituent having no substituent. The alkyl group or the halogenated alkyl group, P" is 2 or 3]. In the above formula (B-2), the alkyl group or the halogenated alkyl group having no substituent of R33 is preferably a carbon number of 1 to 10, The carbon number is preferably from 1 to 8, preferably from 1 to 6. The R33 is preferably a halogenated alkyl group and more preferably a fluorinated alkyl group. The hydrogen atom is preferably fluorinated at 50% or more, more preferably 70% or more, and more preferably 90% or more of the fluorinated group is an aryl group of 16-200830046 R34, such as phenyl or biphenyl ( A ring of an aromatic hydrocarbon such as a biphenyl), a fluorenyl group, a naphthyl group, an anthracyl group or a phenanthroline group, which removes one hydrogen atom and a part of a carbon atom constituting the ring of the aforementioned group. a heteroaryl group obtained by substituting a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, etc., wherein a fluorenyl group is more preferred. The aryl group of R34 may have an alkyl group having 1 to 10 carbon atoms, an alkyl halide group, A substituent such as an alkoxy group may also be used. The alkyl group or the halogenated alkyl group is preferably a carbon number of 1 to 8, more preferably a carbon number of 1 to 4. Further, the halogenated alkyl group is more preferably a fluorinated alkyl group. The alkyl group or the halogenated alkyl group is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 6. R3 5 is preferably a halogenated alkyl group or a fluorinated alkyl group. More preferably, a partially fluorinated alkyl group is preferred. The fluorinated alkyl group in R35 preferably has a hydrogen atom in the alkyl group of 50% or more, more preferably 70% or more. When 90% or more is fluorinated, it is more preferable to increase the acid produced. The most preferred one is a perfluorinated alkyl group in which 100% of hydrogen atoms are replaced by fluorine. In the above formula (B-3), R36 is not The alkyl group or the halogenated alkyl group having a substituent is, for example, the same as the alkyl group or the halogenated alkyl group having no substituent represented by R33 in the above (B-2). The aromatic hydrocarbon group of 2 or 3 of R37 For example, a group obtained by further removing 1 or 2 hydrogen atoms from the aryl group of R34 in the above (B-2), an alkyl group having no substituent or a halogenated alkyl group of R38, for example, the above (B-2) a thiol group having no substituent represented by R35 or The halogenated alkyl group is the same as the content of -17-200830046. p" is preferably 2. Specific examples of the sulfonate-based acid generator (B-1), such as α-(p-toluenesulfonyloxyimido)-benzyl cyanide (cyanide), α-(ρ-chlorophenylsulfonate) Oxyimido)-benzyl cyanide, α-(4-nitrophenylsulfonyloxyimino)-benzyl cyanide, α-(4-nitro-2-trifluoromethylbenzenesulfonyloxy) Imino)-cathyl cyanide, α-(phenylsulfonyloxyimido)-4-chlorobenzyl cyanide, α-(phenylsulfonyloxyimino)-2,4-dichloro Benzyl cyanide, α-(phenylsulfonyloxyimino)-2,6-dichloro-based cyanide, α-(phenylsulfonyloxyimino)-4-methoxyoxycyanate , α-(2-chlorophenylsulfonyloxyimino)-4-methoxybenzyl cyanide, α-(phenylsulfonyloxyimino)-thiazol-2-ylacetonitrile, α-( 4. Dodecylbenzenesulfonyloxyimido)-benzyl cyanide, α-[(ρ-toluenesulfonyloxyimido)-4-methoxyphenyl]acetonitrile, α-[(10 Dialkylbenzenesulfonyloxyimido)-4-methoxyphenyl]acetonitrile, p-toluenesulfonyloxyimido)-4-thiol cyanide, α-(methylsulfonyloxyimino) )-1-cyclopentenylacetonitrile, α-(methylsulfonate -1 -cyclohexenylacetonitrile, α-(methylsulfonyloxyimido)-1-cycloheptyl acetonitrile, α-methylsulfonyloxyimido)-1-cyclooctenylacetonitrile , α-(trifluoromethylsulfonyloxyimido)-1-cyclopentenylacetonitrile, α-(trifluoromethylsulfonyloxyimido)-cyclohexylacetonitrile, α·(ethylsulfonate Oxyimido)-ethylacetonitrile, α-(propylsulfonyloxyimino)-propylacetonitrile, ^-(cyclohexylsulfonyloxyimino)-cyclopentylacetonitrile, cyclohexylsulfonium Oxyimido)-cyclohexylacetonitrile, (-cyclohexylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenyl Acetonitrile, α·(isopropylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α- -18- 200830046 (η-butylsulfonyloxyimino)-1-cyclopentenylacetonitrile , α-(ethylsulfonyloxyimino)-1-cyclohexenylacetonitrile, isopropylsulfonyloxyimido)-1-cyclohexenylacetonitrile, α-(η-butylsulfonate Oxyimido)-1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimino)-phenylacetonitrile, α-(methylsulfonyloxyimino)-ρ-methoxybenzene Acetonitrile, α-(trifluoromethyl Alkylsulfonyloxyimido)-phenylacetonitrile, α-(trifluoromethylsulfonyloxyimido)-ρ-methoxyphenylacetonitrile, (ethylsulfonyloxyimino)-ρ- Methoxyphenylacetonitrile, α-(propylsulfonyloxyimido)-fluorene-methylphenylacetonitrile, α-(methylsulfonyloxyimido)·Ρ-bromophenylacetonitrile, and the like. Further, an oxime sulfonate-based acid generator disclosed in JP-A-9-208 554 (paragraphs [0012] to [0014] [Chem. 18] to [Chem. 19]), WO 04/074242 ( The sulfonate-based acid generator disclosed in Examples 1 to 40) on pages 65 to 85 may also be used in combination. Further, for example, a compound shown below or the like is suitable. -19- 200830046 【化5】

-20- 200830046

1=·|Ό~

C4H9 - 〇2$—Ο—N=C C=N—Ο一 S〇2 One C4H9

CN CN

CF3〇2S—Ο—N=C CN

Ch3o

CH3-C=N-〇S〇2-{CH2)3CH3 CH3-C=N-OS〇2-(CH2)3CH3 200830046 Among the above exemplified compounds, the following four compounds are more preferable. [Chem. 7] C4H9-〇2S—Ο—N:

Ν—0S02——(CH2)aCH3 N-0S02——(CH2)aCH3

The above diazomethane acid generator, for example, bis(phenylsulfonyl)diazomethane, bis(P-toluenesulfonyl)diazomethane, bis(xylsulfonyl)diazomethane, bis(cyclohexyl) Sulfhydryl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(η-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis( Sec-butylsulfonyl)diazomethane, bis(η-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl) Nitrogen methane, bis(n-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert_pentyl) Sulfhydryl)diazomethane, 1·cyclohexylsulfonylbutylsulfonyl)diazotriene, 1-cyclohexylsulfonyl-yl_1_(^1·!:-pentylsulfonyl)diazomethane, L-tert-pentylsulfonyl-l-(tert_butylsulfonyl)diazomethane. The above-mentioned ethylene diterpenoid acid generator, for example, bis-indole-(P-toluenesulfonyl)-dimethylglyoxime, bis--0-(p-toluenesulfonyl)-α-diphenylethylene -22- 200830046 肟, bis-indole-(Ρ·toluenesulfonyl)-α-dicyclohexylethanediamine, bis-indole-(p-toluenesulfonyl)-2,3-pentanedione B Diterpenoid, bis--0-(p-toluenesulfonyl)-2·methyl-3,4-pentanedione ethanedioxime, bis-indolyl-(η-butanesulfonyl)-α-di Methylglyoxime, bis(η-butanesulfonyl α-diphenylglyoxime, bis- 0-(η-butanesulfonyl) α-dicyclohexylethylenedifluorene, bis- 〇·( Η-butanesulfonyl)-2,3-pentanedione ethanedioxime, bis--0-(η-butanesulfonyl)-2-methyl-3,4-pentanedione ethylene肟, double-0-(methanesulfonyl)-"-dimethylglyoxime" bis-indole-(trifluoromethanesulfonyl)-α-dimethylglyoxime, double-0-(1 , 1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis- 0-(tert-butanesulfonyl)-α-dimethylglyoxime, bis-indole- (Perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-indole-(cyclohexanesulfonyl)-α-dimethylglyoxime, double-0-(phenylsulfonate) )-α·Dimethylglyoxime, bis--0-(ρ-fluorophenylsulfonyl)-α-dimethylglyoxime, bis-CKp-tert-butylbenzenesulfonyl)-α - dimethylglyoxime, bis-indole-(xylsulfonyl)-α-dimethylglyoxime, bis--0-(decanesulfonyl)-α-dimethylglyoxime, etc. The above big bismuth acid generator, such as bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonyl Methane, diisopropylsulfonyl methane, bis-indole-toluenesulfonyl methane, bisbenzenesulfonyl methane, etc. The aforementioned /3-ketoflavoric acid generator, such as 2-cyclohexylcarbonyl-2-( ρ-Toluenesulfonyl)propane, 2-isopropylcarbonyl-2-(ρ-toluenesulfonyl)propane, etc., such as the above diterpenoid acid generator, such as diphenyl dinon derivative, dicyclohexyl Anthracene derivatives, etc. -23- 200830046 The aforementioned nitrobenzyl sulfonate acid generator, such as p-toluenesulfonic acid 2,6-dinitrobenzyl ester, p-toluenesulfonic acid 2,4-dinitro Benzyl ester, etc. The aforementioned sulfonate-based acid generator, for example, 1,2,3-tris(methanesulfonyloxy)benzene, 1 , 2,3-tris(trifluoromethanesulfonyloxy)benzene, 1,2,3·tris(p-toluenesulfonyloxy)benzene, etc. The sulfonate of the aforementioned N-hydroxyimine compound An acid generator such as Nucciximide methanesulfonate, N-hydroxybutylimine trifluoromethanesulfonate, N-hydroxybutylimine ethanesulfonate, N-hydroxybutanediamine 1-propane sulfonate, N-hydroxybutaneimine 2-propane sulfonate, N-hydroxybutaneimine 1-pentane sulfonate, N-hydroxybutyrate Diimine imine 1-octane sulfonate, N-hydroxybutaneimine p-tosylate, N-hydroxybutaneimine p-methoxybenzenesulfonate, N-hydroxybutane Imine 2-chloroethane sulfonate, N-hydroxybutylimine benzene sulfonate, N-hydroxybutaneimine 2,4,6-trimethylbenzene sulfonate, N-hydroxyl Butadiene imine 1-naphthalene sulfonate, N-hydroxybutaneimine 2-naphthalene sulfonate, N-hydroxy-2-phenylbutaneimine methane sulfonate, N-hydroxymalay Yttrium imide methane maleimide methane sulfonate, N-hydroxymaleimide ethane sulfonate, N-hydroxy-2-phenyl maleimide methane sulfonate, N-hydroxyl Dimethyleneimine methane sulfonate, N-hydroxypentadienic acid Aminobenzenesulfonate, N-hydroxyindole methanesulfonate, N-hydroxyindole benzsulfonate, N-hydroxyindoleimide trifluoromethanesulfonate, N-hydroxyindole Amine p-toluenesulfonate, N-hydroxynaphthyldimethylimide methanesulfonate, N-hydroxynaphthalene xylene sulfonate, N-hydroxy-5-norbornene-2,3- Dicarboxyimine methane sulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimino trifluoromethanesulfonate, N-hydroxy-5-norbornazole _ 2,3-dicarboxyl Imine ρ-toluenesulfonate and the like. -24- 200830046 (B) Ingredients, one type of these acid generators may be used alone or in combination of two or more. In the present invention, the (B) component is preferably an oxime sulfonate-based acid generator (B-1) having a group represented by the above formula (II). . In the negative-type resist composition for an electron beam of the present invention, the content of the component (B) is, for example, 3 to 15% by mass based on the SiO 2 conversion concentration of the component (A) in the coating liquid for forming a decane-based film. Preferably, it is 5 to 10% by mass. When it is in the above range, the irradiation of the electron beam promotes the formation of Si-O-Si bonds between the components (A), and the photoresist pattern can be easily obtained by development. &lt;Arbitrary component&gt; The negative-type photoresist composition for an electron beam of the present invention may be further added with a mixing component, for example, a contrast enhancer, an organic solvent or the like may be appropriately added. The negative resist composition for an electron beam of the present invention may contain a comparative reinforcing agent. The contrast enhancer can sense light (electron wire) and/or heat, and control the solubility of the formed photoresist film (hardened film), and enhance the contrast by the unevenness of the developed photoresist film. Ingredients. The above-mentioned contrast enhancing agent is not particularly limited as long as it has the above-mentioned function, and it can be appropriately selected from among known compounds by blending the composition of the negative-type resist composition for an electron beam, the type of developing solution, and the like. Specific examples of the contrast enhancer include, for example, a photoacid generator other than the component (B), a thermal acid generator, a photobase generator, a hot base generator, and the like. -25- 200830046 The photoacid generator is not particularly limited as long as it is other than the component (B). For example, a gun salt or the like can be used. Specifically, the aforementioned iron salt is, for example, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium nonafluorobutanesulfonate, tetra-n-butylammonium nonafluorobutanesulfonate, and nonafluorobutanesulfonic acid Phenyl ammonium, tetramethylammonium p-toluenesulfonate, diphenyliodide trifluoromethanesulfonate, p-tert-butoxyphenyl)phenyl iodide, P-toluene Acid diphenyl iodide, p-tert-butoxyphenyl)phenyl iodide, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (ρ-tert-butoxy Phenyl)diphenylphosphonium, bis(p_tert_butoxyphenyl)phenylphosphonium trifluoromethanesulfonate, tris(p_tert_butoxyphenyl)trifluoromethanesulfonate mirror, p-toluenesulfonic acid Phenylhydrazine, p-tert-toluenesulfonic acid (p_tert-butoxyphenyl)diphenylphosphonium, p-toluenesulfonic acid bis(p-tert-butoxyphenyl)phenyl scoop, p-toluenesulfonic acid (p-tert-butoxyphenyl) mirror, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonate Base, tricyclomethanesulfonate cyclohexylmethyl (2-oxocyclohexyl) fluorene, ρ- Cyclohexylmethyl benzenesulfonate (2-oxocyclohexyl) mirror, dimethylphenyl mirror of trifluoromethanesulfonate, dimethylphenyl sulfonate of p-toluenesulfonate, dicyclohexylbenzene trifluoromethanesulfonate Base, p-toluenesulfonic acid dicyclohexylphenylphosphonium, trinaphthyltrifluoromethanesulfonate, trifluoromethanesulfonate cyclohexylmethyl (2-oxocyclohexyl) mirror, trifluoromethanesulfonic acid ( 2-norbornylalkyl)methyl(2-oxocyclohexyl)anthracene, ethylene bis[methyl(2-oxocyclopentyl)phosphonium trifluoromethanesulfonate (sulfonate)], 1,2'- Naphthylcarbonylmethyltetrahydrothiophenyl trifluoromethanesulfonate and the like. The aforementioned thermal acid generator is a compound which can induce heat to generate an acid. -26- 200830046 The thermal acid generator is not particularly limited, and for example, it may contain at least one 2,4,4,6-tetrabromocyclohexadienone, benzoquinone tosylate, 2-nitrobenzyl A toluenesulfonate, a composition other than an alkyl sulfonate or a thermal acid generator thereof, or the like is used as a usual thermal acid generator. The photobase generator is a compound which can induce light (electron rays) to form a base. The photobase generator is not particularly limited, and is, for example, a photoactive urethane such as triphenylmethanol, a benzyl carbazate or a benzoguanyl carbazate; a fluorene-aminoformamidine; Hydroxyguanamine, hydrazine-aminoformamidine, arylamine sulfonamide, phthalamide and other decylamines such as N-lactone and N-(2-allylacetylene) decylamine; oxime ester, α- Aminoethyl benzene, cobalt complex, and the like. Among them, 2-nitrobenzylcyclohexylaminoformate, triphenylmethanol, hydrazine-aminoformamidine hydroxy guanamine, hydrazine-aminocarbamidine, [[(2,6-dinitro) Benzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoinyl)-1 -Methyl-1-morpholine ethane, (4-morpholinylbenzoyl)-1-benzyl-1-dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine Preferably, hexaammine (III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone or the like is preferred. The above-mentioned hot base generating agent is a compound which can induce heat to generate a base. The hot base generator is not particularly limited, and for example, 1-methyl-1-(4-biphenyl-yl)ethylcarbamate or 1,1-dimethyl-2-cyano group can be used. a urethane derivative such as ethyl urethane; a urea derivative such as urea or N,N-dimethyl- Ν'-methyl urea; 1,4-dihydronicotinium amide or the like Dihydropyridine derivative; quaternized ammonium salt of organic decane or organoborane; dicyandi-27-200830046 decylamine and the like. Others, such as bismuth trichloroacetate, methyl hydrazine triacetate, potassium trichloroacetate, cesium phenyl sulfonate hydrazine, hydrazine P-chlorophenyl sulfonyl hydrazide, P-methanesulfonyl phenyl sulfonyl sulfhydryl Barium acetate, potassium phenylpropanoate, barium phenylpropanoate, phenylpropanoid, P-chlorophenylpropanoate, P-phenyl-bis-phenylpropanoate, benzene Tetramethylammonium sulfosuccinate, tetramethylammonium phenylpropanoate, and the like. The addition amount of the contrast enhancer in the negative-type resist composition for an electron beam of the present invention is 0.1 to 30% by mass based on the SiO 2 conversion concentration of the component (A) in the coating liquid for forming a decane-based film. Preferably, it is preferably 1 to 15% by mass, preferably 5 to 10% by mass. When the amount of the contrast enhancer added is 0.1% by mass or more, the effect of the contrast enhancer can be sufficiently obtained, and the resist pattern formed by the developer treatment is sufficiently contrasted. Further, when the amount of the contrast enhancer added is 30% by mass or less, the storage stability of the negative-type photoresist composition for an electron beam can be improved, and the film reduction amount of the exposed portion during development can be prevented from being lowered, thereby preventing the film from being reduced. The contrast is reduced. The negative-type photoresist composition for an electron beam of the present invention is intended to improve the uniformity of coatability and film thickness, and therefore it is preferable to contain an organic solvent (hereinafter referred to as "(S) component). For the (S) component, the ingredients generally used in the past can be used. Specifically, for example, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, etc. Alkyl alcohol esters such as methyl-3-methoxypropionate and ethyl-3-ethoxypropionate; multivalent of ethylene glycol-28-200830046, diethylene glycol, propylene glycol, etc. Alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl Multivalents such as ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Alcohol derivatives; fatty acids such as acetic acid and propionic acid; ketones such as acetone, methyl ethyl ketone and 2-heptanone. The (S) component may be used singly or in combination of two or more. The amount of the component (S) is not particularly limited, and the concentration of the component other than the component (S) (solid component) is preferably 5 to 100% by mass, more preferably 20 to 50% by mass. When it is in the above range, the coating property to the substrate or the like can be improved. Further, in the present invention, various additives such as other resins, surfactants, and adhesion aids may be added to the extent that the effects of the present invention are not impaired. The additive can be suitably selected in accordance with the function desired. In the case where a surfactant is added, the coating property of the negative-type photoresist composition for an electron beam can be improved, and the flatness of the obtained photoresist film can also be raised upwards, such as Β Μ - 1 0 0 0 (trade name; Β Μ Chemie company); Megefis F14 2 D, with F172, with F173, and with F183 (above, trade name; Dainippon Ink Chemical Industry Co., Ltd.); Prola FC -135, with FC-170C, with FC-43 0, and with FC-43 1 (above, trade name; Sumitomo 3 Μ (share) system); Shaflon S-1 1 2, same as S -1 1 3 , with S-131, with S-141, and with S-145 (above, trade name; Asahi N-29-200830046 sub-share); SH-28PA, SH-190, SH-193, SZ-6032 , fluorine-based surfactants such as SF-8428, DC-57, and DC-190 (above, trade name; Toray Polyoxane Co., Ltd.). The ratio of the surfactant in the negative-type photoresist composition for the electron beam is preferably 5 parts by mass or less, more preferably 0.01 part by mass or less, based on 1 part by mass of the component other than the surfactant (solid content). ~ 2 parts by mass. Further, when a tackifier is used, the adhesion of the negative-type photoresist composition for an electron beam to a substrate or the like can be improved. The tackifier is preferably a decane compound (functional decane coupling agent) having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group or an epoxy group. Specific examples of the aforementioned functional decane coupling agent include, for example, trimethoxyalkyl benzoic acid, 7-methene propylene oxy methoxy methoxy trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, 7-Iocyanatepropyltriethoxydecane, r-glycidoxypropyltrimethoxydecane, /3-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. In the negative-type photoresist composition for an electron beam, the use ratio of the tackifier is 1 〇0 parts by mass relative to the component other than the tackifier (solid content), preferably 20 parts by mass or less, more preferably 〇. · 〇 5 to 10 parts by mass, preferably 1 to 1 0 parts by mass. <<Formation Method of Photoresist Pattern>> The method for forming a photoresist pattern of the present invention is a step -30-200830046 for forming a photoresist film on a substrate by using the negative-type photoresist composition for an electron beam of the present invention. a step of exposing the photoresist film to a step of developing the photoresist film to form a photoresist pattern. The method of forming the photoresist pattern can be carried out, for example, in the following manner. In other words, the negative-working photoresist composition for the electron beam is applied to a substrate such as a tantalum wafer by a spin coater (spin coating method) or the like at a temperature of 100 to 250 ° C. For example, after baking for 20 to 200 seconds, preferably 60 to 150 seconds, p〇st-apply bake (PAB) is applied to the electronic wire, for example, using an electron beam drawing machine or the like. The reticle pattern is expected to be selectively exposed. Thereafter, post exposure bake (PEB) can be carried out at a temperature of from 1 Torr to 25 ° C for a period of from 20 to 200 seconds, preferably from 60 to 150 seconds. In the present invention, PEB (bake after exposure) may or may not be performed. Next, it is subjected to development treatment using an alkali developing solution, for example, a 5 to 20% by mass aqueous solution of tetramethylammonium hydroxide. In this way, a photoresist pattern of a faithful response mask pattern can be obtained. Further, an organic or inorganic antireflection film may be provided between the substrate and the coating layer of the photoresist composition. As described above, the present invention can provide a novel method of forming a negative resistive composition for an electron beam and a resist pattern using the negative resistive composition for an electron beam. Further, in the negative-type photoresist composition for an electron beam of the present invention, for example, a negative-type photoresist composition for an electron beam is applied onto a substrate, and a photoresist film (cured film) formed by baking after baking (PAB) is applied. ), has excellent film stability (PCD) after coating film formation -31 - 200830046, and has good solubility to alkali developing solution. The photoresist pattern obtained by using the negative-type photoresist composition for an electron beam of the present invention is highly suitable as a model for engraving (i m p r i n t) lithography (original). [Embodiment] [Embodiment] Next, the present invention will be described in more detail by way of examples, but the present invention is not limited by the examples. &lt;Preparation of Negative Photoresist Composition for Electron Wire&gt; (Example 1) 73.9 g (0.45 mol) of triethoxydecane having a SiO 2 conversion concentration of 2% by mass was dissolved in propylene glycol dimethyl ether 67 2.9 g (6.8 mol), it was stirred and dissolved. Next, a solution obtained by mixing 24.2 g (1.34 mol) of pure water and 5 ppm of concentrated nitric acid was slowly added dropwise thereto with stirring, and then stirred for about 3 hours, after which it was allowed to stand at room temperature. During the day, a solution was prepared. This solution was subjected to vacuum distillation under reduced pressure of 120 to 140 mmHg and 40T for 2 hours to produce a coating liquid for forming a film of a ceramsite film having a concentration of SiO 2 of 1% by mass and an ethanol concentration of 1% by mass. In the coating liquid for forming a decane-based film obtained above, 0.7 parts by mass of an oxime sulfonate-based acid generator represented by the following chemical formula is added to 100 parts by mass of the coating liquid (this coating is applied) The concentration of Si 〇 2 in the solution of the triethoxy decane condensate in the liquid was 7% by mass) to prepare a negative-type photoresist group for electron beams -32-200830046. 【化8】

丫 "Ν-. One S〇2 - (CF2)4-H &lt;Formation of Photoresist Pattern> The negative-type photoresist composition for electron wires of Example 1 obtained above was applied to 8 inches by spin coating. After the wafer was mounted on the wafer, it was subjected to calcination (PAB) for 120 seconds under a temperature of 18 Å to form a photoresist film (hardened film) having a film thickness of 30 Onm. Next, the photoresist film (cured film) obtained above was subjected to an electron beam drawing machine (Hitachi HL-8 00D, 70 kV accelerating voltage), and after drawing an electron beam, at 23 ° C, 1 〇 mass% of NaOH 4 The methylammonium (TMAH) aqueous solution was developed for 60 seconds, washed with water, and dried by vibration. It was confirmed that the negative-type photoresist composition for an electron beam of Example 1 of the present invention can form an L & S pattern of 500 nm by the above-described method for forming a photoresist pattern. &lt;Evaluation of film stability (PCD) after coating film formation> The negative-type photoresist composition for electron beam of Example 1 was used, and the coating liquid for forming a decane-based film was used alone (hereinafter, referred to as "comparison" Example 1"), a photoresist film (cured film) was formed in the same manner as above. Next, the photoresist film was immersed in the water under the conditions shown in Tables 1 to 3 immediately after the formation of the light-33-200830046 film (Table 1) and after 15 days (Table 2). After 10 seconds (Table 3), development was carried out for 60 seconds at 23 ° C using a 10% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), washed with water, and shaken. The film thickness at this time was measured, and PCD evaluation was performed. The results are shown in Tables 1 to 3. [Table 1] Film thickness (nm) after development of the photoresist film immediately after development of the photoresist film Example 1 218 0 Comparative Example 1 215 0 [Table 2] After the formation of the photoresist film, after 15 Film thickness (nm) at the time of development processing in the future After development of the photoresist film, Example 1 218 0 Comparative Example 1 215 Residue was confirmed [Table 3] After the photoresist film was formed, the photoresist film was immersed in water for 10 seconds. After that, the film thickness (nm) at the time of developing treatment was formed after the photoresist film was formed in the immersion water for 10 seconds, and then developed. Example 1 218 222 0 Comparative Example 1 215 221 135 From the results of Tables 1 to 3, the present invention was carried out. In the negative electrode resist composition of the electron beam of Example 1, it was confirmed that the film thickness after development was -34-200830046 degrees in both cases, and it was excellent in solubility to the unexposed portion developing solution. PCD. Further, in Comparative Example 1 which is different from the present invention, it was confirmed that the residue was found in the development treatment after 15 days (Table 2), and the residual film was also found in the development treatment after immersing in water for 1 second (Table 3). ), with a poor PCD. In the negative-type photoresist composition for an electron beam of the present invention, for example, a negative-type photoresist composition for an electron beam is applied onto a substrate, and after being coated, a photoresist film (cured film) formed by baking (PAB) is baked. It has excellent film stability (PCD) after film formation, and has good solubility to alkali developers. Further, the photoresist pattern obtained by using the negative-type photoresist composition for an electron beam of the present invention is very suitable as a model for etching lithography (original). Therefore, the present invention has a very high industrial price. -35-

Claims (1)

200830046 X. Patent Application No. 1 A negative-type photoresist composition for an electron beam, which comprises a hydrolyzate of an alkoxydecane compound represented by the following formula (I) and a formula (I) At least one compound (A) selected from the group consisting of the condensate of the alkoxydecane compound shown, and the nonionic acid generator (B), R1, OR2)4-n (1) [In the formula (I), R1 is a hydrogen atom or a monovalent organic group, R2 is a monovalent organic group, and η is an integer of 1 to 3]. 2. The negative-type photoresist composition for an electron beam according to the first aspect of the invention, wherein the non-ionic acid generator (Β) is an oxime sulfonic acid comprising a group represented by the following formula (Π). Ester-based acid generator (Β-1), [Chem. 2] -C=N-Ο-S〇2-R31 R32 (II) [In the formula (II), R31 and R32 each independently represent an organic group]. 3. A method for forming a photoresist pattern, comprising the steps of: forming a photoresist film on a substrate by using a negative photoresist composition for an electron beam according to claim 1 or 2; The step of exposing the resist film to the step of developing the photoresist film to form a photoresist pattern. -36- 200830046 succinctly, there is no simple: the number is the map of the map element: the table pattern represents the book without a set of two fingers c C VIII. If there is a chemical formula in this case, please reveal the best display of the characteristics of the invention. Chemical formula