TW200914994A - Radiation-sensitive composition and compound - Google Patents

Abstract

Disclosed is a radiation-sensitive composition containing (a) a compound represented by the general formula (1) below, and (b) a radiation-sensitive acid generator which generates an acid when irradiated with radiation. (1) (In the formula, R represents hydrogen or the like; R1 represents a methylene group or the like; Y represents an alkyl group or the like; and q represents 0 or 1.)

Description

200914994 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to a linear composition of sensitive radiation, and more particularly to an electron beam (hereinafter sometimes referred to as "EB") or extreme ultraviolet light (hereinafter sometimes referred to as "EB") Hereinafter, it is sometimes referred to as "EUV") a positive type sensitive radiation linear composition suitable for forming a fine pattern and a compound relating to a linear composition capable of obtaining the sensitive radiation. [Prior Art] A field of fine processing represented by the manufacture of integrated circuit components In order to obtain a higher integrated body circuit and rapidly develop the miniaturization of the design rule in the lithography process, the development of the lithography process which can stabilize the fine processing is strongly promoted. However, in the past, for example, a lithography process using KrF or ArF excimer lasers is difficult to form a fine pattern with high precision. Therefore, recently, in order to achieve fine processing, a lithography etching process using an electron beam instead of a KrF, ArF excimer laser has been proposed. As the electron beam resist material used in the photolithography etching process using this electron beam, a methacrylic main chain-cut positive photoresist such as ΟΡΜΗA (polymethyl methacrylate) has been proposed (for example, reference) Patent Documents 1 and 2); (2) Chemically amplified type positive light having a polyhydroxystyrene resin (KrF excimer resin) and a novolac (i-line resin) and an acid generator protected by an acid-cleavable group A resist (for example, refer to Non-Patent Document 1); (3) A positive and negative resist having an organic low molecular weight containing a film of calixarene, fuUerene or the like to form an amorphous layer of 200914994 (amorphous) (for example, refer to Patent Documents 3 to 11), a photoresist using a polyhydric phenol compound (for example, refer to Patent Documents 12 to 13), etc. Further, it is also proposed to contain 1,3,5-parallel [4-( 2-Tertiaryoxycarbonyloxy)phenyl]benzene is a chemically amplified photoresist having an organic low molecular weight other than calixarene or fullerene (for example, refer to Non-Patent Document 2). [Patent Document 1] JP-A-2000-147777 [Patent Document] Japanese Patent Laid-Open Publication No. Hei No. Hei 1 1 - 296 No. 1 (Patent Document 3) Japanese Patent Publication No. Hei 1 1 - 3 2 2 6 5 6 [Patent Document 4] Japanese Patent Laid-Open No. 1 1 - 7 2 9 1 6 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 12] Japanese Laid-Open Patent Publication No. Hei. No. 2006-235340 [Non-Patent Document 1] Proc. SPIE. VOL 5376 75 7-764 (2004) [Non-Patent Document 2 ] J. Photo Sci. and Tech. VOL12 No2 375-376 (1999) [Summary of the Invention] -6- 200914994 However, in the above-mentioned electron beam photoresist material, the positive photoresist of (丨) is resistant to etching, There is a problem in sensitivity, and it is difficult to put it into practical use. For example, in order to improve the sensitivity, it is proposed to use a polytetradecyl α-chloromethylstyrene or to introduce an atom which is easily cut by an electron beam at the end of the resin. Ν, 0, S) by (Patent Documents 1 and 2), but that although some degree of improved sensitivity, but has not reach the practical level of sensitivity in the etching resistance aspect. Further, the chemically amplified positive photoresist (e.g., Non-Patent Document No.) of (2) has a high sensitivity, but has a problem of minute surface unevenness when a fine pattern is formed due to the use of the resin. Here, the term "small surface unevenness" means the edge of the interface between the photoresist and the substrate, which is due to the characteristics of the photoresist, and is irregularly changed in the direction perpendicular to the linear direction, and is viewed from directly above the pattern. The edges look bumpy. Since the unevenness is accidentally transferred by the etching step using the photoresist as the photomask, the electrical characteristics are unexpectedly deteriorated, and the yield is lowered. In particular, the improvement of minute surface unevenness in an ultrafine field of 0 · 15 μm or less becomes an extremely important issue. In the photoresist of (3), the photoresist of the calixarene (for example, Patent Documents 3 to 5) is excellent in etching resistance, but the molecular interaction between the molecules is very strong, and the solubility in the developing solution is deteriorated. Therefore, a satisfactory pattern cannot be obtained. Further, although a compound using a calixarene derivative has been reported (for example, see Patent Document 6), the performance of fine surface unevenness is not clear. Further, a photoresist using fullerene (for example, Patent Documents 7 to 1 1) has a good etching resistance, but the coating property and the sensitivity are not reached. Further, 1,3,5-gin[4-(2-t-butoxycarbonyloxy)phenyl]benzene is used as an organic low molecular compound having film forming ability other than calixarene and fullerene. An amplifying type resist (for example, Non-Patent Document 2) is insufficient in coating property, adhesion to a substrate, and sensitivity, and does not reach a practical degree. Further, a photoresist of a polyphenol (for example, a patent) is used. Document 1 2~1 3) Although the degree of solution is good, the sensitivity does not reach the practical level. The present invention has been made in view of the problems of the prior art, and as a subject thereof, it is possible to form a film which can effectively induce electron beams or extreme ultraviolet rays, fine surface irregularities, etching resistance, excellent sensitivity, and high A sensitive radiation linear composition of a chemically amplified positive type resist film which forms a fine pattern accurately and stably, and a compound which can obtain the linear composition of the sensitive radiation. As a result of extensive review of the above-mentioned problems, the inventors of the present invention have found that the above-mentioned problems can be attained by a compound having a specific structure and a radiation-sensitive linear composition containing the compound and a radiation-sensitive linear acid generator. invention. That is, the present invention provides a compound shown below and a radiation sensitive linear composition. [1] A sensitive radiation linear composition comprising (a) a compound represented by the following formula (1), and (b) a sensitive radiation linear acid generator which generates an acid by irradiation with radiation, 200914994 [Chem. 1]

(In the formula (1), R is each independently a hydrogen atom or a decanoic acid-dissociating group. R 丨 Each other: a substituted or unsubstituted methyl group or a substituted: unsubstituted extension Institutional, Y is independent of each other as a carbon number. Substituted = Γ-based, carbon-substituted or unsubstituted dilute base: == Γ unsubstituted alkynyl, carbon number-substituted or kijiu: ; 基未: The substituted or unsubstituted courtyard oxygen of 1 to 10. The substituted or unsubstituted phenoxy group, q ί skin this independent 0 or !) [Overview (1) sensitive radiation linear composition, The compound represented by the above formula is a compound represented by the following formula (2): 200914994 [Chemical 2]

(2) (In the formula (2), R is each independently a hydrogen atom or a monovalent acid dissociable group, and R1 is independently a substituted or unsubstituted methyl group or a carbon number of 2 to 8 substituted or not Substituted alkylene). [3] The sensitive radiation wire composition of the above [2], wherein the compound represented by the above formula (2) is a compound represented by the following formula (3):

(3) (In the formula (3), each R is independently a hydrogen atom or a monovalent acid dissociable group). The sensitive radiation linear composition according to any one of the above [1] to [3] wherein the acid dissociable group is represented by the following general formula (4-1) or (4-2) Foundation: [Chemical 4]

R4 (4-1) (4-2) (In the formula (4_1), R2 is a linear, branched or cyclic group having 1 to 40 carbon atoms which may be substituted or unsubstituted with a substituent which may contain a hetero atom. The alkyl group having a structure of η is an integer of 0 to 3, and in the formula (4-2), R3 is a linear one having a carbon number of 1 to 40 which is substituted or unsubstituted with a substituent which may contain a hetero atom. An alkyl group having a branched or cyclic structure, and R 4 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. [5] The linear composition of the radiation of the above [4], wherein R2 in the above formula (4-1) is a third butyl group, a 2-methyl-2-adamantyl group, a 2-ethyl group-2 -adamantyl, 1-ethylcyclopentyl or 1-methylcyclopentyl, and η is 0 or 1, wherein R3 in the above formula (4-2) is adamantyl and R4 is a hydrogen atom, or R4 is a methyl group and R3 is a 2-methyl-2-goldenyard group, or R4 is a methyl group and R3 is a 2-ethyl-2-adamantyl group. [6] The sensitive radiation linear composition according to [5] above, wherein the (b) radiation sensitive linear acid generator is at least selected from the group consisting of a key salt, a diazo compound, and a sulfonimide compound. One. [7] The sensitive radiation linear composition according to any one of [1] to [6] above, which further contains (c) an acid diffusion controlling agent. -11 - 200914994 [8] - a compound represented by the following formula (1), [Chemical 5]

(In the general formula (1), one of the -m哄-derived groups, at least one of which is an acid-dissociable group, which is independently substituted or unsubstituted by a methyl group or a carbon number of 2 to 8 or The unsubstituted exudate is substituted or unsubstituted alkyl having a carbon number of 1 to 10, and the substituted or unsubstituted alkenyl group of Y 2:10, carbon number 2 to 丨Substituted: substituted: a substituted alkynyl group, a carbon number H. a substituted or unsubstituted aralkyl group: a substituted or unsubstituted alkoxy group having no carbon number, or a substituted:: substituted The phenoxy group, q is independent of each other as ruthenium or osmium). [9] The compound of the above [8], which is represented by the following formula (2): -12- 200914994 [Chem. 6]

(2) (In the formula (2), each R is independently a hydrogen atom or a monovalent acid dissociable group, and at least one of R is an acid dissociable group, and R 1 is independently substituted or unsubstituted. a substituted or unsubstituted alkyl group having 2 to 8 carbon atoms. [10] The compound of the above [9], which is represented by the following formula (3):

(3)

(In the formula (3), R is each independently a hydrogen atom or a monovalent acid dissociable group, and at least one of R -13 to 200914994 is an acid dissociable group) [11] A compound of the above [1〇] Wherein the above acid-dissociable group is a group represented by the following formula (4-1) or (4-2):

(In the formula (4-1), R2 is a hospital group having a linear, branched or cyclic structure having a carbon number of 1 to 4 Å which may be substituted or unsubstituted with a substituent which may contain a hetero atom, η is An integer of 0 to 3, and in the formula (4-2), R3 is a linear, branched or cyclic structure having a carbon number of 1 to 40 substituted or unsubstituted with a substituent which may contain a hetero atom. The alkyl group, R4 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The sensitive radiation linear composition of the present invention is a chemically amplified positive type which can be formed into a film which can be effectively induced by an electron beam or an extreme ultraviolet ray, has a small surface unevenness, an etching resistance, is excellent in sensitivity, and can form a fine pattern with high precision and stability. The photoresist film is effective. The compound of the present invention is a chemically amplified positive type resist which can be formed into a film which can be effectively induced by an electron beam or an extreme ultraviolet ray, has a small surface unevenness, an etching resistance, is excellent in sensitivity, and can form a fine pattern with high precision and stability. The film is sensitive to the linear composition of the radiation and exerts its effect. . BEST MODE FOR CARRYING OUT THE INVENTION The present invention is not limited to the following embodiments, and the present invention is not limited to the scope of the present invention. Based on the well-known knowledge, the following embodiments are appropriately changed, modified, etc., but it is to be understood that these are within the scope of the present invention. π] Compound: The compound of the present invention is a compound represented by the following formula (1) (hereinafter sometimes referred to as "(a) compound"). The compound (a) is a compound having an acid-dissociable group (modified) having a structure in which at least one of the hydroxyl groups bonded to the benzene ring has a structure protected by an acid dissociable group. According to this, the (a) ft compound is an acid-dissociable group which is decomposed by an acid, and the acid-dissociable group is removed to become an alkali-soluble one.

1 and R are unsubstituted. In the formula (1), each of R is independently a hydrogen atom or a monovalent acid dissociable group. At least one of them is an acid dissociable group. R1 is independent of each other by substituting the methyl group of -15-200914994 or the carbon number of 2~8. The n n 4 unsubstituted extension is independently taken as the carbon number 丨~丨0, γ 丨, - The substituted or unsubstituted alkenyl group of the substituted alkyl group, such as the number 2~1〇峨2~1 〇, the 炔Bf· + 代代的基基' carbon number 7~1() Substituted or unsubstituted oxycarbons of substituted or unsubstituted aralkyls, substituted or unsubstituted, or substituted or not taken

Ethyloxy. q are independent of each other or 1. R is preferably a structure represented by the following formula (2): [Chemical 1 0]

In the formula (2), each R is independently a hydrogen atom or a monovalent acid dissociable group, and at least one of R is an acid dissociable group 'R1 is independently substituted or unsubstituted methyl or carbon number 2 The substituted or unsubstituted alkyl group of ～8 is more preferably a compound represented by the following formula (3): -16- 200914994 [Chemical 1 !]

In the formula (3), 'R is each independently a hydrogen atom or a monovalent acid dissociable group' and at least one of R is an acid dissociable group. The above compound (a) can be obtained, for example, by producing a precursor obtained by introducing at least one acid dissociable group into the precursor. First, a compound represented by the following formula (5) and a compound represented by the following formula (6) can be, for example, in a solvent, in the presence of a catalyst, at a reaction time of 12 hours to 50 hours, and a reaction temperature of 60 to 9 (TC). Under the conditions of dehydration condensation, a precursor for the production of the above compound (a) is obtained. The above catalyst can be exemplified by, for example, an acid catalyst. For the catalyst, for example, hydrochloric acid or the like can be used. The amount of the catalyst used is, for example, isophthalic acid. 2 eq of concentrated hydrochloric acid in a reaction system of 20 mM phenol (functional equivalent: 4 〇 millimolar) and it hexamethylenediamine 5 mM (functional equivalent: 10 mmol) in ι·5 ml -17- 200914994

[Chemical Formula 1 3] 〇HC - (CH2)4 - CHO (6) Further, the compound represented by the above formula (5) (hereinafter sometimes referred to as "compound (5)") and the above formula (6) The mixing ratio of the compound (hereinafter sometimes referred to as "compound (6)") is not particularly limited, but is solid from the viewpoint of yield with respect to 1 mol of the compound (6), and the compound (5) Fortunately between 8 · 00 ~ 1.00 Mo's better between 6.00 ~ 2.00 Mo, and preferably between 5.00 ~ 3.00 Mo. If the compound (5) does not reach ι·〇〇莫耳, the yield of the target compound may be lowered. On the other hand, if it exceeds 8.00 moles, the yield of the target compound may be lowered. Further, the concentration of the substrate in the reaction solution (the total concentration of the compound (5) and the compound (6)) is not particularly limited, but from the viewpoint of the yield, it is preferably 2 Å/L or more and more preferably 4 Mole / liter or more, and preferably in the range of 4 ~ 1 〇 Mo / L. If the monomer concentration is less than 2 mol/liter, the yield of the target compound is lowered. As the solvent, for example, ethanol, isopropanol, n-propanol or the like can be used, and among them, in terms of obtaining a high yield, ethanol is preferred. The amount of solvent used is, for example, resorcinol 20 mM (functional equivalent: 4〇-18-200914994 mM) and 1,6-hexanediamine 5 mM (functional equivalent: 1 〇 millimolar) The reaction system was 4.5 ml. Next, the precursor is added to a compound having a group represented by the following formula (4-1) or formula (4-2) in the presence of an acid or a base in a solvent at a reaction time of 1 hour to 2 0. The reaction of the reaction was carried out under the conditions of an hour temperature of -2 0 to 1 〇〇 to obtain the above compound (a). Further, the mixing ratio of the above-mentioned precursor to the compound having a group represented by the formula (4-1) or the formula (4-2) is not particularly limited, but in terms of yield, it is 'relative to 1 mol. The precursor having a compound represented by the above formula (d) or formula (4-2) is preferably 1 mol or more, more preferably 5 to 2 mol. If the compound having a group represented by the above formula (';!) or the formula (4-2) is less than 1 mol, the yield of the target compound may be lowered. On the other hand, if all of the hydroxyl groups of the precursor are protected, there is a case where the surface roughness is deteriorated. R in the above formula (3) is each independently a hydrogen atom or a monovalent acid dissociable group. Wherein at least one of 'R is preferably a hydrogen atom. The structure of the above acid-dissociable group is not particularly limited, but is preferably, for example, a group represented by the following formula (4-1) or (4-2). Further, when R in the above formula (3) is substituted with a plurality of acid dissociable groups, 'R may be independently a group represented by the following formula (4-1) or (4-2): -19- 200914994 [化1 4]

R4 (4-1) (4-2) In the formula (4-1), R2 is a linear or branched carbon having a carbon number of 1 to 40 which is substituted or unsubstituted with a substituent which may contain a hetero atom. The alkyl group 'η of the cyclic structure is an integer of 〇~3. Further, in the formula (4-2), R3 is an alkyl group having a linear, branched or cyclic structure having a carbon number of 丨~4〇 substituted or unsubstituted with a substituent which may contain a hetero atom, R 4侄It is not a hydrogen atom or an alkyl group having a carbon number of 1 to 5. The base of the above formula (4-1) can be exemplified by, for example, a group represented by the following formula (7-1) to (7-9):

(7-3) (7-4) 20- 200914994

(7-7) [Chemical 1 6 (7-8) R5 [Chemical 1 7] 〇R5 (7-9) II I , -COC-R5 R5 (with the above formula (7-1)~(7-9 In the group indicated, R5 is an alkyl group having 1 to 5 carbon atoms, and η is an integer of 1 to 3). Further, the group represented by the above formula (7-1) to (7-9) is preferably a group represented by the formula (7-1), (7-8) or (7-9). R5 in the above formula (7-1) to (7-9) is a lower alkyl group (a hospital having a carbon number of 1 to 5), and specific examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. , 正-21 - 200914994 A lower linear or branched alkyl group such as butyl, isobutyl, tert-butyl, pentyl, isopentyl or neopentyl. Preferably, these are methyl or ethyl, more preferably fluorenyl. Further, R2 in the above formula (4-1) is specifically preferably 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 1-ethylcyclopentyl or 1 -methylcyclopentyl, tert-butyl. Further, the group represented by the above formula (4-1) is specifically preferably 2-methyl-2-goldenyloxycarbonylmethyl, 2-ethyl-2-goldenyloxy oxime Methyl, 1-ethylcyclopentyloxycarbonylmethyl, 1-methylcyclopentyloxycarbonylmethyl, tert-butoxycarbonylmethyl, tert-butoxycarbonyl. The group represented by the above formula (4-2) can be exemplified by, for example, the groups represented by the following formulae (8-1) to (8-14). [化1 8]

-22 - 200914994

(8-5) (8-6)

[化1 9]

(8-13) (8-14) -23 - 200914994 In the above formula (8_1) to (8-14), R4 and R5 are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As the alkyl group having 1 to 5 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. may be exemplified. Lower linear or branched alkyl. Further, in the above formulae (8-1) to (8-10), m is an integer of 0 to 2, and preferably 0 or 1. The group represented by the above formula (4-2) is specifically preferably a 2-Goldanyloxymethyl group, the following formula (9), the following formula (1〇) or the following formula; (1) υ Table base: [Chemical 2 0]

[Chem. 2 1]

(9) (10)

(11) [2] Sensitive radiation linear composition: The linear composition for sensitive radiation of the present invention is a linear acid generator containing the above-mentioned (a) compound and -24-200914994 (b) by irradiation of radiation to generate an acid. The linear composition of the radiation of the present invention is excellent in uranium engraving resistance by containing the compound (a) and containing a compound having a benzene ring skeleton. Further, since the compound (a) contained in the linear composition for sensitive radiation of the present invention is a non-resin low molecular compound, it does not cause aggregation due to the resin, and therefore has excellent surface unevenness. Further, the sensitive radiation linear composition of the present invention is excellent in sensitivity because it introduces the same acid dissociable group as the chemical amplification type resist. Therefore, in the lithography etching process, the electron beam or the extreme ultraviolet ray can be effectively sensed, the fine surface irregularities, the etching resistance, and the sensitivity are excellent, and the fine pattern can be formed with high precision and stability. [2-1] Sensitive radiation linear acid generator: The above (b) sensitive radiation linear acid generator is produced in a linear composition of sensitive radiation when a linear composition of sensitive radiation is irradiated by an electron beam or the like in a photolithography etching process. The acid substance can dissociate the acid dissociable group of the above compound (a) by the action of the acid. (b) The radiation-sensitive linear acid generator is preferably at least one selected from the group consisting of a key salt, a diazomethane compound, and a sulfonamide compound in view of good acid generation efficiency, heat resistance and the like. Moreover, these may be used alone or in combination. The key salt can be exemplified by, for example, an iodine salt, a phosphonium salt, a money salt, a diazo salt, a pyridyl salt, and the like. Specific examples of the key salt are triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium benzenesulfonate, triphenylsulfonium 10-camphorsulfonate Acid salt, triphenylsulfonium perfluoro-n-octane sulfonate, -25- 200914994 triphenylsulfonium 4-trifluoromethylbenzenesulfonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium perfluoride Benzene sulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-2-(tetracyclo[4,4,0,125,17'1()]dodecane-8-yl)ethane Sulfonate, triphenylsulfonium 1,1-difluoro-2-(bicyclo[2.2.1]heptan-2-yl)ethanesulfonate; (4-tert-butoxyphenyl)diphenyl Base trifluoromethanesulfonate, (4-tert-butoxyphenyl) diphenylphosphonium nonafluorobutane sulfonate, (4-tert-butoxyphenyl)diphenylphosphonium perfluoride N-octane sulfonate; (4-hydroxyphenyl)diphenylphosphonium trifluoromethanesulfonate, (4-hydroxyphenyl)diphenylphosphonium nonafluorobutane sulfonate' (4-hydroxybenzene) Diphenylphosphonium perfluorooctane sulfonate, (4-hydroxyphenyl)diphenylphosphonium 1 〇 camphorsulfonate, (4-hydroxyphenyl)diphenylphosphonium n-octane sulfonate Salt; ginseng (4-methoxyl) a trifluoromethanesulfonate, a quinone (4-methoxyphenyl)phosphonium nonafluorobutane sulfonate, a ginseng (4-methoxyphenyl)phosphonium perfluorooctane sulfonate,参(4-methoxyphenyl)锜ι〇_ camphorsulfonate; (4-fluorophenyl)-phenyl mirror trifluoromethanesulfonate, (4-fluorophenyl)diphenylphosphonium Fluorine butane sulfonate, (4-fluorophenyl)diphenylphosphonium 10-camphorsulfonate; ginseng (4-fluorophenyl)phosphonium trifluoromethanesulfonate, ginseng (4-fluorophenyl)锍9-fluoro-n-butane sulfonate, ginseng (4-fluorophenyl) 锍10-camphorane sulfonate, ginseng (4-fluorophenyl) fluorene p-toluene sulfonate, ginseng (4-trifluoromethyl) Phenyl) fluorene trifluoromethanesulfonate; 2,4,6-trimethylphenyldiphenylphosphonium trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylphosphonium 2, 4·difluorobenzenesulfonate, 2,4,6-trimethylphenyldiphenylphosphonium 4-trifluoromethylbenzenesulfonate; diphenyliodopronium trifluoromethanesulfonate, diphenyl Iodine hexafluoro-n-butane-26- 200914994 sulfonate, diphenyl iodine perfluoro-n-octane sulfonate, diphenyl iodine gun 1 〇-camphor sulfonate, diphenyl iodine octane Sulfur Bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, bis(4-tert-butylphenyl)iodoferric hexafluoro-n-butane sulfonate, double (4_third Butylphenyl) iodine perfluoro-n-octane sulfonate, bis(4-t-butylphenyl) iodine 10-camphorsulfonate, bis(4-t-butylphenyl) iodine Octanesulfonate; (4-methoxyphenyl)phenyl iodide trifluoromethanesulfonate, (4-methoxyphenyl)phenyl iodide nonafluorobutane sulfonate, (4 _Methoxyphenyl)phenyl iodide perfluoro-n-octane sulfonate; (4-fluorophenyl)phenyl iodide trifluoromethanesulfonate, (4-fluorophenyl)phenyl iodide Fluorine n-butane sulfonate, (4-fluorophenyl)phenyl iodine gun 10-camphorsulfonate; bis(4-fluorophenyl)iodotrifluoromethanesulfonate, bis(4-fluorophenyl) Iodine nonafluoro-n-butane sulfonate, bis(4-fluorophenyl) iodine gun 10-camphorsulfonate: bis(4-chlorophenyl)iodotrifluoromethanesulfonate, double (4_ Chlorophenyl) iodine-free nonafluoro-n-butane sulfonate 'bis(4-chlorophenyl) iodine perfluoro-n-octane sulfonate, bis(4-chlorophenyl)iodine 10-camphor Salt, bis(4-chlorophenyl)iodonium n-octane sulfonate, bis(4-chlorophenyl)iodonium 4-trifluoromethylbenzenesulfonate, bis(4-chlorophenyl)iodine Perfluorobenzenesulfonate; bis(4-trifluoromethylphenyl)iodotrifluoromethanesulfonate, bis(4-trifluoromethylphenyl)iodonium nonafluoro-n-butanesulfonate, double (4-trifluoromethylphenyl)iodoferrin perfluoro-n-octane sulfonate, bis(4-trifluoromethylphenyl)iodyl-n-dodecylbenzenesulfonate, bis(4-trifluoro) Methylphenyl) iodine p-toluenesulfonate, bis(4-trifluoromethylphenyl)iodobenzenesulfonate, bis(4-trifluoromethylphenyl)iodo-27- 200914994 iron 1 〇 - camphor sulfonate, bis(4-trifluoromethylphenyl) iodine gun n-octane sulfonate, bis(4-trifluoromethylphenyl) iodine gun 4-trifluoromethylbenzene sulfonate, Bis(4-trifluoromethylphenyl)iron iodide perfluorobenzene-propionate, preferably triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoro-n-butyl sulfonate, Triphenylphosphonium 10 - camphorsulfonate, (4-hydroxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl)diphenylphosphonium Butane sulfonate, bis(4-methoxyphenyl)phosphonium trifluoromethanesulfonate, ginseng (4-methoxyphenyl)phosphonium nonafluorobutane sulfonate, (4-fluorophenyl) Diphenylphosphonium trifluoromethanesulfonate, (4-fluorophenyl) diphenyl mirror, nonafluorobutane sulfonate, 2,4,6-trimethylphenyldiphenyl mirror, trifluoromethanesulfonate Acid salt, 2,4,6-trimethylphenyldiphenylphosphonium 2,4-difluorobenzenesulfonate, 2,4,6-trimethylphenyldiphenyl vegetable 4-trifluoromethyl Benzene sulfonate, diphenyl iodine: fluorene difluoride compound, diphenyl iodine hexafluoro n-butane sulfonate, diphenyl iodine gun 1 〇-camphor sulfonate, double (4- Tert-butylphenyl)iodotrifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate, bis(4-t-butylphenyl)iodine Key 10 - camphor sulfonate '(4-fluorophenyl)phenyl iodide trifluoromethanesulfonate, (4-fluorophenyl)phenyl iodide nonafluoro-n-butane sulfonate, (4-fluoro Phenyl)phenyl iodide 10-camphorsulfonate, bis(4-fluorophenyl)iodotrifluoromethanesulfonate, bis(4-fluorophenyl)iodoferrocene n-fluorobutane sulfonate, Double (4· Fluorophenyl) iodine 10 10-camphorsulfonate, ginseng (4-trifluoromethylphenyl)phosphonium trifluoromethanesulfonate. These may be used singly or in combination of plural kinds. The diazomethane compound can be exemplified by, for example, bis(trifluoromethanesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(3,3-dimethyl-1,5-dioxa Spiro[5.5]dodecane-8-sulfonyl)diazomethane, bis(1,4-dioxa-28- 200914994 spiro[4 5]decane-7-sulfonyl)diazomethane, double (T-butylsulfonyl) diazomethane and the like. Preferred among these are bis(cyclohexylsulfonyl)diazomethane and bis(3,3-dimethyl-1,5-dioxaspiro[5.5]dodecane-8-sulfonyl) Nitrogen methane, bis(1,4-dioxaspiro[4.5]decane-7-sulfonyl)diazomethane. These may be used singly or in combination of plural kinds. The sulfonimide compound is exemplified by, for example, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenide, N-(trifluoromethyl) Sulfhydryloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenine, N-(trifluoromethylsulfonyloxy)bicyclo[2.2. 1] heptane-5,6-oxy-2,3-dicarboxylimenide, N-(10-camphorsulfonyloxy) amber imine, N-(10-camphorsulfonyloxy酞醯imino, N-( 10-camphorsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-(10- Camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylimenimimine, N-(10-camphorsulfonyloxy)naphthylimine, N-[(5-methyl-5-carboxymethylbicyclo[2.2.1]heptan-2-yl)sulfonyloxy]succinimide; ^^-(n-octylsulfonyloxy) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenine, N-(n-octylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy -2,3-dicarboxylimine imine, N-(perfluorophenylsulfonyloxy)bicyclo[2_2.1]hept-5-ene-2,3-dicarboxyarmine, N-(all Fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxylimine imine, N-(perfluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylimenide, -29 - 200914994 N-(nonafluoro-n-butylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenide, N-(nonafluoro-n-butylsulfonyloxy) -7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenine, N-(nonafluoro-n-butylsulfonyloxy)bicyclo[2.2.1]g Alkane-5,6-oxy-2,3-dicarboxylimenide, N-(perfluoro-n-octylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-(perfluoro-n-octylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-(all Fluoranthylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylimenide. Preferred among these are N-(trifluoromethylsulfonyloxy)bicyclo[2.2.n hept-5-ene-2,3-dicarboquinone imine, N-(10-camphorsulfonyloxy) Alkyl iminoimine, N-[(5-methyl-5-carboxymethylbicyclo[2.2.1]heptan-2-yl)sulfonyloxy]succinimide. These may be used singly or in combination of plural kinds of bismuth (b) radiation sensitive linear acid generator in an amount of preferably 0.1 to 30 parts by mass, more preferably 0.5 to 2 parts by mass per part by mass of the compound (a). 5 parts by mass. If the weight of the (b)-sensitive ray generator is less than 1 part by mass, the sensitivity and developability may be lowered. On the other hand, when it exceeds 30 parts by mass, the transparency of the radiation pattern, the shape of the pattern, the heat resistance, and the like may be lowered. [2-2] (Citrate diffusion inhibitor: The sensitive radiation linear composition of the present invention preferably further contains (c) an acid diffusion inhibitor. (c) The acid diffusion inhibitor can control exposure to (b) sensitive radiation The acid produced by the linear acid generator diffuses in the photoresist film and has a component that inhibits undesired chemical reactions in the unexposed regions. By adjusting -30-200914994 with such a (C) acid diffusion inhibitor It can improve the storage stability of the linear composition of the obtained sensitive radiation and further enhance the resolution as a photoresist and suppress the resist pattern line caused by the change of the placement time (PED) before the heat treatment from exposure to exposure. The sensitive radiation linear composition which is excellent in process stability is obtained, and the (c) acid diffusion controlling agent is preferably, for example, a nitrogen-containing organic compound or a photosensitive basic compound. The above nitrogen-containing organic compound can be exemplified by, for example, the following. a compound represented by the formula (12) (hereinafter referred to as "nitrogen-containing compound (i)"), a compound containing two nitrogen atoms in the same molecule (hereinafter referred to as "nitrogen-containing compound (ii)") a polyamine compound or a polymer having three or more nitrogen atoms (hereinafter referred to as "nitrogen-containing compound (iii)"), a guanamine-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, or the like. 2 3] R6 (12) R6-N-R6 (In the above formula (12), each R6 is independently a hydrogen atom, a linear, branched or cyclic alkyl group which may be substituted, and a substituted aromatic group Or a substituted aralkyl group. The nitrogen-containing compound (i) is preferably, for example, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, cyclohexylamine, etc. Mono(cyclo)alkylamines; di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-decylamine, di-n-decylamine, Di(cyclo)alkylamines such as cyclohexylmethylamine, dicyclohexylamine; triethylamine, tri-n-propylamine, tri-31 - 200914994 n-butylamine, tri-n-pentylamine, tri-n-hexylamine , tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, tri-n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, tricyclohexylamine, etc. Amines; substituted amines such as triethanolamine; aniline, N-methylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4 _Nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2,4,6-tri-t-butyl-N-methylaniline, N-phenyldiethanolamine, 2,6-diisopropyl The aromatic amine nitrogen-containing compound such as aniline is preferably, for example, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine. 4,4 diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4,-diaminodiphenylamine , 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)_2_(4-aminophenyl)propane, 2-(4-aminophenyl)-2- (3-hydroxyphenyl)propane, 2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane, iota, 4-bis[1-(4-aminophenyl)-b methyl Benzene Benzene, 3-bis[helium 4-aminophenyl)-1-methylethyl]benzene, bis(2-dimethylaminoethyl)ether, bis(2-diethylamine) Ethyl ethyl ether, 1-(2-hydroxyethyl)-2-imidazolidinone, 2- Salicin, N,N,N,,N,-肆(2-hydroxypropyl)ethylenediamine, N,N,N',N,',N,,-pentamethyldiethylidene Amines, etc. The nitrogen-containing compound (iii) is preferably a polymer such as polyethylenimine, polyisopropylamine or 2-dimethylaminoethylpropenamide. Butoxycarbonyldi-N-t-butoxyamine, N-third of the above-described guanamine-containing compound except for, for example, N-tert-n-octylamine, N-second butoxy-based di-n-decyl Amine, carbonyl di-n-decene base, N-t-butoxycarbonylbicyclohexyl-32- 200914994 butoxycarbonyl-1 -adamantylamine, n-t-butoxycarbonyl _ 2 - 金刚院Alkylamine, N-tert-butoxycarbonyl-N-methyl_1.-Goldenamine, (S)-(-)-1-(Tertibutoxycarbonyl)-2-pyrrolidinemethanol, + Third butoxycarbonyl)-2-thiazolidine methanol, N-tert-butoxycarbonyl-4-hydroxypiperidine, N-tert-butoxycarbonylpyrrolidine, N-tert-butoxylate Piperazine, hydrazine, hydrazine, bis-tert-butoxycarbonyl-bumantylamine, hydrazine, hydrazine-di-t-butoxycarbonyl-hydrazine-methyl-1-adamantylamine, hydrazine-third butyl Oxycarbonyl _4,4'-diaminodiphenylmethane, anthracene, fluorene, -di-t-butoxycarbonyl hexamethylenediamine, hydrazine, hydrazine, hydrazine, Ν'-four-third Butoxycarbonylhexamethylenemonoamine, hydrazine, Ν'_di-t-butoxycarbonyl-1,7-diaminoheptane, hydrazine, Ν'_di-butoxycarbonyl _ 1,8 - Diaminooctane, anthracene, anthracene, -di-tert-butoxy-p-group-1,9-diaminodecane, anthracene, anthracene, -di-tert-butoxycarbonyldiaminodecane, anthracene, Ν'-Di-tert-butoxycarbonyl-1,12-diaminododecane, anthracene, Ν'-di-t-butoxycarbonyl- 4,4,-diaminodiphenyl-based, Ν-Tertialbutylbenzimidazole, Ν-Tertibutoxycarbonyl·2-methylbenzimidazole, Ν-Second butoxycarbonyl-2-phenylbenzimidazole, etc. An amine-based compound containing a -butoxyalkyl group, further preferably a formamide, Ν-methylformamide, Ν'Ν_dimethylformamide, acetamide, Ν-methyl Ethylamine, hydrazine, hydrazine - dimethyl acetamide, acetophene, benzamide, pyrrolidone, hydrazine _methylpyrrolidone, hydrazine-ethenyl-b-adamantylamine, isoniazid Cyanate citrate (2-hydroxyethyl ester) and the like. The above urea compound is preferably, for example, urea, methyl urea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenyl. Base urea, tri-n-butyl urea, and the like. The above nitrogen-containing heterocyclic compound is, for example, imidazole, 4-methylimidazole, 4-methyl-33-200914994-2-phenylimidazole 'benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2- Imidazoles such as methylimidazole and benzyl-2-methyl-1H-imidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinic acid decylamine, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, 2 Pyridines such as 2',6',2"-terpyridine, and piperazines such as piperazine and 1-(2-hydroxyethyl)piperazine are preferably pyrazine, pyrazole, pyridazine and quinoxaline. , hydrazine, pyrrolidine, piperidine, piperidine ethanol, 3-piperidinyl-1,2-propanediol, morpholine, 4-methylmorpholine, 1-(4-morpholinyl)ethanol, 4-acetyl Basomomorpholine, 3-(N-morpholinyl)-1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, etc. The photosensitive basic compound can be efficiently decomposed into a neutral segment corresponding to the exposed region, and is not decomposed in the unexposed portion. Residual component. The photosensitive basic compound is more effective than the non-photosensitive basic compound because the exposed portion (exposure region) can effectively utilize the acid produced, thereby improving the sensitivity. The kind of the compound is not particularly limited as long as it has the above properties. For example, a compound represented by the following formula (1 3 - 1 ) and formula (13-2) can be suitably used: -34- 200914994

(In the above formula (13-1) and formula (13-2), r7 to ru, respectively, a halogen atom, an alkyl group having a carbon number of the substituent hiO, an alicyclic hydrocarbon group of a substituent, and X· represents 0H. -, r12OH·, R. X—the R12 represents a monovalent organic group). The alkyl group of R7 to R11 which may have a carbon number of a substituent may be, for example, methyl, ethyl, n-butyl, t-butyl, trifluoromethyl, methoxy, di-butoxy, or the third The butoxymethylmethyloxy group 'R7 to R11 is preferably a hydrogen atom or a third butyl group. Further, the monovalent organic group of R12 may, for example, be an aryl group which may have an alkyl group and may have a substituent. Further, as the above X-, OH-, CH3COO·, or a compound: a nitrogen atom or a '2C〇〇-, such as a fluorine atom, etc., may be suitably used. And there are substituents. The following formula shows -35- 200914994 [Chemical 2 5]

COO ^γ-0Η ^^^coo" A preferred example of the above-mentioned photosensitive basic compound is a diphenyl sulfonium compound (a compound represented by the above formula (1 3 - 1 )), and an anion portion thereof. The fraction (X·) is OH-, CH3COO· or a compound represented by the following formula: [Chem. 2 6] ^^COO-

[Chem. 2 7] COO

Further, the above (c) acid diffusion controlling agent may be used singly or in combination of two or more. (C) The amount of the acid diffusion controlling agent is preferably 15 parts by mass or less with respect to 100 parts by mass of the compound (a) is more preferably 0: 001 to 10 parts by mass, more preferably -36 to 200914994 0.005 to 5 parts by mass. . If the amount of the (c) acid diffusing agent is more than 15 parts by mass, the sensitivity of the resist or the deterioration of the exposed portion of the exposed portion may be lowered. Further, if the amount of the (c) acid diffusion controlling agent is less than 1 part by mass, the process condition ' decreases as the pattern shape or size of the photoresist is lowered. [2-3] Other components: The linear composition of the sensitive radiation of the present invention is preferably obtained by dissolving the above compound (a), (b) a radiation sensitive linear acid generator, and (c) an acid diffusion controlling agent in a solvent. . In other words, it is preferred to contain a solvent as another component. Further, the sensitive radiation linear composition of the present invention may be formulated with various additives such as a surfactant, a sensitizer, and an aliphatic additive as other components. The solvent is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, 2-heptanol and cyclohexanone (hereinafter referred to as "solvent 1"). A solvent other than the above solvent 1 (hereinafter referred to as "other solvent") can also be used as the solvent. Further, the solvent 1 and other solvents may be used in combination. Other solvents may, for example, be propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol monoisobutylene. Propylene glycol monoalkyl ether acetate such as ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monobutyl ether acetate; 2-butanone, 2-pentanone, 3-methyl Keto butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-octanone, etc. Linear or branched ketones; cyclopentanone, 3-methylcyclopentanone, 2-methylcyclohexanone-37- 200914994, 2,6-dimethylcyclohexanone, isophorone, etc. Ketones; 2-hydroxymethyl ester, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate, 2-hydroxyisopropyl ester, 2-propionic acid n-butyl vinegar '2-propionic acid 2-hydroxypropionic acid such as isobutyl ester, 2. second butyl propionate, and tert-butyl 2-hydroxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-_3-ethoxy propionate alkyl ester such as methyl ethoxylate '3-ethoxypropionate, n-propanol, isopropanol, n-butanol Tert-butanol, cyclohexanol, alcohol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, alcohol mono-n-butyl ether, diethylene glycol dimethyl ether, diethyl Glycol diethyl diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol single positive Propionate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, toluene, xylene, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxyacetate , 2-hydroxy-3-methylbutyric acid methyl ester, 3· butyl butyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methylmethoxybutyl propionate , 3-methyl-3-methoxybutyl butyrate, ethyl ester, n-propyl acetate, n-butyl acetate, methyl acetoxyacetate, ethyl acetate, methyl pyruvate, pyruvate Ester, N-methylpyrrole, N,N-dimethylformamide, N,N-dimethylacetamide, benzylethyldi-n-hexyl ether, diethylene glycol monomethyl ether, diethyl Glycol monoethyl ether acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, Diethyl oxalate, diethyl maleate, -butyrolactone, carbene carbonate, propylene carbonate, and the like. Hydroxyalkyl propionate propionate propylene glycol diethyl ether, monomethyl ether mono-n-ethyl ethoxy-3-acetic acid ethyl hydrazinyl ether, hexanoic acid ethyl-38-200914994 among these other solvents Preferred as linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, alkyl 2-hydroxypropionates, alkyl 3-alkoxypropionates, r-butyl Lactones, etc. The above other solvents may be used singly or in combination of two or more. When a solvent mixture of the solvent 1 and another solvent is used as the solvent, the ratio of the other solvent is preferably 50% by mass or less, more preferably 40% by mass or less, and most preferably 30% by mass or less based on the total of the solvent. The sensitive radiation linear composition of the present invention usually has a total solid content concentration of from 1 to 50% by mass, more preferably from 1 to 25% by mass, based on the use thereof. Therefore, the U) compound, (b) the radiation-sensitive linear acid generator, (c) the acid diffusion controlling agent, and optionally other additives (excluding the solvent) are dissolved in the solvent so as to become the total solid concentration. After the solution, it is preferably filtered through a filter having a pore diameter of, for example, about 0.2 μm to obtain a composition solution composed of a linear composition of a sensitive radiation. Further, the surfactant contained as the other component is a component which exhibits an effect of improving coatability, storage property, developing property and the like. Such surfactants can be exemplified by, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-decyl phenyl ether , non-ionic surfactants such as polyethylene glycol dilaurate, polyethylene glycol distearate, and the following trade names ΚΡ 3 4 1 (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW No. 75, POLYFLOW Νο·95 (manufactured by Kyoeisha Chemical Co., Ltd.), F TOP EF301, F TOP EF303, F TOP EF3 52 (manufactured by TORKEMU PRODUCT), ΜEGAFAX F171, MEGAFAX F173 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), -39- 200914994 FLORARD FC43 0, FLORARD FC 4 3 1 (manufactured by Sumitomo 3 M), AS AHIGU ARD AG710, SURFLON S-3 82 'SURFLON SC-101 ' SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC -105, SURFLON SC-106 (made by Asahi Glass Co., Ltd.). These interface activities may be used singly or in combination of two or more. The interfacial activity may be used singly or in combination of two or more. The amount of the surfactant to be formulated is preferably from 0. oo to 2 parts by mass based on 1 part by mass of the compound (a). The sensitizer is a sensitizer that exhibits absorption of radiation energy and transmits its energy to (b) a sensitive radiation linear acid generator, whereby the effect of adding the amount of the acid generated has a sensitivity to enhance only the linear composition of the sensitive radiation. The effect of the degree. The sensitizers can be exemplified by oxazoles, acetophenones, benzophenones, naphthalenes, phenols, hydrazine, Eosin, rosin, and pyrenes. Terpenoids, phenothiazines, etc. Further, these sensitizers may be used singly or in combination of two or more. The amount of the sensitizer to be added is preferably from 0.1 to 10 parts by mass per 100 parts by mass of the (a) compound. Further, by blending a dye or a pigment, the latent image of the exposed portion becomes visible, and the effect of halating during exposure can be alleviated. The adhesion to the substrate can be improved by blending the subsequent additive. Further, the sensitive radiation linear composition of the present invention may be added with an alicyclic additive having an acid dissociable group or an alicyclic additive having no acid dissociable group. The alicyclic additive having an acid dissociable group or the alicyclic additive having no acid dissociable group is a component having an effect of further improving dry etching resistance, pattern shape, adhesion to a substrate of -40 to 200914994, and the like. The alicyclic additives may, for example, be, for example, 1-adamantanecarboxylic acid, 2-adamantanone, tert-butyl 1-adamantanecarboxylate, tert-butoxycarbonylmethyl 1-adamantanecarboxylate, 1 - adamantyl alcohol a-butyrolactone, 1,3-adamantane dicarboxylic acid di-t-butyl ester, 1-adamantane acetic acid tert-butyl ester, 1-adamantane acetic acid tert-butoxycarbonyl methyl ester, Adamantane derivatives such as di-n-butyl 1,3-adamantyl diacetate, 2,5-dimethyl-2,5-di(adamantanecarbonyloxy)hexane; third deoxycholate Ester, tert-butoxymethyl methyl deoxycholate, 2-ethoxyethyl deoxycholate, 2-cyclohexyloxyethyl deoxycholate, 3-oxocyclooxycholate Deoxycholate esters such as hexyl ester, tetrahydropyranyl deoxycholate, and valerate deoxycholate; third butyl choate, third butoxycarbonyl thiocyanate Ester, 2-ethoxyethyl lithic acid, 2-cyclohexyloxyethyl lithate, 3-oxocyclohexyl lithate, tetrahydropyranyl lithate, lithocholic acid Rock cholate such as valonolactone; dimethyl adipate, diethyl adipate, dipropylene adipate An alkyl formate such as an ester, di-n-butyl adipate or di-tert-butyl adipate, or 3-[2-hydroxy-2,2-bis(trifluoromethyl)ethyl]tetracycline [ 4.4.0.12 '5.17'1()] decane, etc. These alicyclic additives may be used singly or in combination of two or more. The blending amount of the alicyclic additive is preferably from 0.5 to 20 parts by mass based on 100 parts by mass of the (a) compound. When the amount of the alicyclic additive is more than 20 parts by mass, the heat resistance as a photoresist may be lowered. Further, the additives other than the above may be exemplified by an alkali-soluble resin, a low molecular alkali solubility control agent having an acid dissociable protecting group, an antihalation agent, a storage stabilizer, an antifoaming agent, and the like. -41 - 200914994 [3] Method for forming photoresist pattern: The sensitive radiation linear composition of the present invention is particularly useful as a chemically amplified photoresist. The above chemically amplified photoresist is obtained by exposing an acid to the (b) sensitized cation-based acid generator to cause the acid-dissociating base of the (a) compound to be exchanged to generate an alkali-soluble portion, and the result is The exposed portion of the photoresist has a high solubility for the image forming liquid, and the exposed portion is dissolved in the alkali developing solution to remove a positive resist pattern. When the photoresist pattern is formed by the sensitive radiation linear composition of the present invention, it is coated on a substrate such as a sand wafer or an aluminum-coated wafer by a suitable coating method such as spin coating, casting coating or roll coating. The composition solution described above is formed to form a photoresist coating film, and a pre-heat treatment (hereinafter referred to as "PB") is carried out as appropriate to expose the photoresist coating film so as to form a specific photoresist pattern. At this time, the radiation used may be appropriately selected such as K r F excimer laser (wavelength 248 nm), EUV (extreme ultraviolet ray, wavelength 13 nm), etc. X-rays such as far-ultraviolet rays or synchrotron radiation, etc. Particle beam, etc. Further, the exposure conditions such as the amount of exposure are appropriately selected in accordance with the composition of the radiation-sensitive resin composition, the type of the additive, and the like, even if it is exposed by immersion. In the present invention, it is preferred to carry out heat treatment (hereinafter referred to as "P E B") after exposure. By the PEB, the detachment of the acid dissociable group of the compound (a) can be smoothly carried out. The heating condition of P E B varies depending on the composition of the linear composition of the sensitive radiation, but it is usually preferably from 30 to 200 ° C, more preferably from 50 to 170 ° C. In order to maximize the potential of the linear composition of the sensitive radiation, the present invention can form an organic or inorganic system on the substrate to be used, as disclosed in Japanese Patent Publication No. 6-1 2452. Anti-reflection film. In addition, in order to prevent the influence of an alkaline impurity or the like contained in the atmosphere, a protective film can be provided on the photoresist film as disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei. In addition, these techniques can also be used in combination. Next, the exposed photoresist film is developed to form a predetermined photoresist pattern. The developing solution used for development is preferably, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, or the like. N-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo [5.4.0] -7 - An aqueous alkaline solution in which at least one of a basic compound such as undecene or 1,5-diazabicyclo[4·3·0]-5-decane is dissolved. The concentration of the above alkaline aqueous solution is preferably 10% by mass or less. If the concentration of the alkaline aqueous solution exceeds 1% by mass, the non-exposed portion is also dissolved in the developing solution. Further, the developing liquid is preferably ΡΗ8 to 14, more preferably ρ Η 9 〜1 4 〇 Further, for example, an organic solvent may be added to the developing liquid composed of the above aqueous alkaline solution. The above organic solvent can be exemplified by a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone or 2,6-dimethylcyclohexanone. Classes; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, cyclopentanol, cyclohexanol, anthracene, 4-hexanediol, 1,4-hexanedimethanol Ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate, n-butyl acetate, isoamyl acetate; aromatics such as toluene and xylene - 43 - 200914994 hydrocarbons, or phenol, acetonitrile, and Methylformamide and the like. These organic solvents may be used singly or in combination of two or more. The amount of the organic solvent to be used is preferably 100 parts by volume or less based on 1 part by volume of the aqueous alkaline solution. When the amount of the organic solvent used exceeds 100 parts by volume, the developmental property is lowered. Further, a surfactant may be added in an appropriate amount in the developing solution composed of the aqueous test solution. Further, it can be washed with water and dried after development in a developing liquid composed of an alkaline aqueous solution. [Embodiment] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited by the examples. In addition, in the examples and comparative examples, "parts" and "%" are based on the quality unless otherwise specified. [Example 1] (Synthesis of 1,6-hexanedialdehyde) 40 g (1.8 mol) of pyridine chlorate pyridine salt (PCC) as an oxidizing agent was mixed with 400 g of tannin (300 mesh) and pulverized After suspending in 2.6 liters of dichloromethane, a solution of 72 g (600 mmol) of 1,6-hexanediol dissolved in 500 ml of dichloromethane was added, and stirring was carried out at room temperature for 2 hours. After the completion of the reaction, 5 liters of diethyl ether was added to the system. The diethyl ether layer was recovered by decantation, and the solvent was evaporated under reduced pressure. Subsequently, a silica gel chromatography (dissolved solvent: diethyl ether) was carried out, and the solvent was evaporated under reduced pressure, and then purified under reduced pressure to give 5 3 g of a colorless transparent liquid, yield 74%. -44 - 200914994 The liquid obtained was measured by IR and 1 η-nmr, and it was confirmed that the following formula (〇 indicates 1,6-hexanedialdehyde (boiling point: 40.5 to 41.1 ° (: (2. 1111111))) The results of 1H-NMR measurement are listed below. [Chemical 2 8] Formula (c)

OHaC-CHb2-(CHc2)rCHbrCHaO IR (film, cm_1) : 2925 ' 2853, and 2712〇CH) ' 1730 ' 17 12〇C = 0) 'H-NMR (400MHz, CDC13, TMS), δ (ppm) : l_26(s, 4.0H, Hc), 4.17 (m, 4.0H, Hb), 9.76 (bs, 2.0H 'H) [Example 2] (Synthesis of calixarene dimer compound) In a volume of 1 liter eggplant bottle, 22 g (200 mM: functional group equivalent 400 mil) of meta-benzoquinone is dissolved in ethanol, and further 15 ml of hydrochloric acid as a catalyst is added, and then cooled in ice. 5.8 g (50 mmol: functional group equivalent of 100 mmol) of 1,6-hexanedialdehyde was added dropwise. Subsequently, it was heated in 80 ml of ethanol at 80 ° C for 48 hours to obtain a red suspension. After completion of the reaction, the reaction mother liquid was poured into diethyl ether to precipitate a solid. The obtained solid was dried under reduced pressure for 24 hours to obtain 6.7 g of a red solid, yield 44%. The structure of the obtained red solid was confirmed by MALDI-TOF-MS (laser ionization time-of-flight type -45 - 200914994 supported by model SHIMAZU/KRATOS Matrix, KOMPACT MALDI IV tDE, manufactured by Shimadzu Corporation) IR (NICOLET 3) 80 FT-IR, manufactured by Shimadzu Corporation) and ιΗ_NMR (model JNM-ECX-5400P, manufactured by JEOL Ltd.). The results are listed below. [化2 9]

He

He (14) IR(cm'') : 3 26 9( v OH) , 293 3 R 2 8 5 9( v CH) , 192〇, 1 500, and 1 443 ( v C = C aromatic) *H -NMR (400MHz, DMSO-d6, TMS), δ (PPm) · 1.06~2.35(b,32.OH > Ha,Hb), 4.05~4.22(m,8.〇H,Hc) ,6.14(bs , 8_0H, aromatic He), 6_91 (bs, 8_0H, aromatic H < i), 9.1 3 (m, 1 6.0H, OHf) mass analysis (MALDI-TOF MS) measured enthalpy (m/z) 1195.22 [M + H] + Calculated 値 (m/z) 1194.32 [M + H] + -46- 200914994 The following compound (A-1) to be synthesized as the compound represented by the above formula (1) ((a) compound) A-2), and the following compounds (A_3) to (A-4) were used for comparison. [Example 3] Synthesis of Compound (A-1) by adding 3 g of the above calixarene dimer compound (a) and 0.64 g of tetrabutylammonium bromide (TBAB) to 30 ml of pyridine to make calixarene After the dimer compound (a) was dissolved, 4.4 g of dibutyl butyl dicarbonate (DiBoc) was slowly added dropwise under ice cooling, and stirred at room temperature for 24 hours. After completion of the reaction, the mother liquid was diluted with chloroform, washed three times with 1 N hydrochloric acid and once with water, and the organic layer was dried using a drying agent such as anhydrous magnesium sulfate, filtered and then concentrated, then hexane: ethyl acetate = 1 : 4 was purified as a distillate on a silica gel column to obtain 1.5 g of a white solid, yield 30%. The obtained white solid was determined by IR measurement and W-NMR, and it was confirmed that R in the formula (1) was a calixarene dimer compound of a third butoxycarbonyl group, and the protection ratio was confirmed (in the calixarene dimer compound) The ratio of the hydrogen atom of the phenolic hydroxyl group substituted by the third butoxycarbonyl group was 40%. The results of IR measurement and 1H-NMR measurement are as follows: IRCcm·1) : 298 1 , 2934 and 2864 ( CH), 1 760 ( v C = 0), 1615, 1 5 92 and 1 497 (vC = C fang Family), 1371〇t-butyl), 1272 and 1 1 4 3 (y C - Ο - C ether) 'H-NMR (400MHz) - DMSO-d6 > TMS : ά (ppm): 0.86~2.01 ( m, 89.6H, tert-butyl H, -CH2(CH2)2CH2-), 3.79~4·12 (m,8·0H,>CH-), 6_81~7.13 (m,16.0H, aromatic- 47-200914994 Η), 8.33 〜1 0.22 (m, 9.6 Η, OH) [Example 4] Synthesis of Compound (A-2) 3 g of the above calixarene dimer compound (a), 〇·64 g IV After adding butyl ammonium bromide and adding 30 g of 1-methyl-2-pyrrolidone, the mixture was stirred at 70 ° C for 1 hour. Subsequently, 2.8 g of potassium carbonate was added and stirred at 70 ° C for 1 hour. Subsequently, 3.9 g of butyl bromoacetate dissolved in 10 g of 1-methyl-2-pyrrolidone was slowly added, and stirred at 60 ° C for 6 hours. After cooling to room temperature, extraction was carried out with water/dichloromethane, followed by washing twice with 100 ml of a 3 wt% aqueous solution of oxalic acid, followed by washing twice with 100 ml. The aqueous layer was discarded and the organic layer was dried over magnesium sulfate. After the hexane:ethyl acetate = 1:1 was purified as a distillate through a silica gel column to give 3.8 g of Compound (A-2). After the 1H-NMR analysis, the protection ratio of the compound (A-2) (the ratio of the hydrogen atom of the phenolic hydroxyl group in the compound (A-2) to the third butoxycarbonylmethyl group was 40% [Example 5] Synthesis of Compound (A-5) 3.0 g of the above calixarene dimer compound (a) and 0.65 g of tetrabutylammonium bromide were added together in 30 ml of pyridine, thereby allowing a calixarene dimer compound ( a) After dissolution, 13 g (60 mmol) of dibutyl tricarbonate (DiBoc) was slowly added dropwise under ice cooling, and stirred at room temperature for 24 hours. After the reaction, it was diluted with chloroform. The mother liquor is washed three times with 1N hydrochloric acid, once with tap water, and the organic layer is dried with a desiccant such as anhydrous magnesium sulfate. After filtering the 'dry' sputum, it is concentrated to 1 (0, as a good solvent for chloroform and as a weak The hexane of the solution -48-200914994 was subjected to reprecipitation treatment to obtain 3.7 g of a white solid in a yield of 52%. After the 1H-NMR analysis, the protection ratio of the compound (A-5) (the compound (A-5)) The ratio of the hydrogen atom of the phenolic hydroxyl group substituted by the third butoxycarbonylmethyl group is 100%. [Example 6] Comparative Synthesis Example 1 Compound (A-3), Compound (A-4): 3.8 g of the compound (A-4') was dissolved in 30 ml of tetrahydrofuran, and 5.6 ml of triethylamine and 0.25 g of 4-dimethylaminopyridine were added. The mixture was stirred at room temperature for 5 minutes to dissolve. 6. 6 g of di-tert-butyl dicarbonate dissolved in 1 ml of tetrahydrofuran was slowly added dropwise, and stirred at 6 (TC for 7 hours), and tetrahydrofuran was distilled off under reduced pressure. Extraction with 50 ml of dichloromethane, purification and separation with a hexane:ethyl acetate = 5:1 as a distillate on a silica gel column to obtain 1.8 g of the following compound (A-3), 3.6 g of the following compound (A- 4). [Chemical 3 0]

(A-4') [Chem. 3 1]

-49- 200914994

(A-4) [Example 7] Comparative Synthesis Example 2 Resin (A-6) containing an acid-dissociable group: 10 g of polyhydroxystyrene (VP 8 000, manufactured by Japan Soda Corporation (Mw9000'Mw/Mn) = ll)) A butyl acetate 20% solution was slowly added dropwise with 5.50 g of dibutyltributate dicarbonate and 2.8 g of triethylamine, and the reaction solution was stirred at 60 ° C for 7 hours. Subsequently, a large amount of water was added to the above reaction solution, and the reprecipitation purification operation was repeated. Subsequently, drying under reduced pressure was carried out to obtain 12.0 g of a polyhydroxystyrene (A-6) oxime protected by a third butoxycarbonyl group (Example 8) to give 1 part of the compound (A-1), 9 parts of triphenylsulfonium trifluoromethanesulfonate (referred to as "B-1" in Table 1) as (b) a radiation-sensitive linear acid generator, and 1 part as a (c) acid diffusion control agent Base amine (denoted as "C-1" in Table 1), 600 parts of ethyl lactate as a solvent (denoted as "D-1" in Table 1), and 1 500 parts of propylene glycol monomethyl ether acetate (Table) 1 is indicated as "D-3"), and the mixture was filtered through a membrane filter having a pore size of 200 ηηη to obtain a composition solution (linear radiation sensitive composition). Next, in the CLEAN TRACK ACT-8 manufactured by Tokyo Electronics Co., the composition solution was spin-coated on a tantalum wafer, and then PB (heat treatment) was performed at 130 ° C for 90 seconds to form a film thickness l. A photoresist of 〇〇nm (linear composition of sensitive radiation) is coated. Subsequently, the resist film was irradiated with an electron beam using a simple electron beam scanning-50-200914994 painting device (manufactured by Hitachi, Ltd., type "HL800D", output; 50 KeV, current density: 5.0 amp/cm2). After electron beam irradiation, P E B was performed at 130 ° C for 90 seconds. Subsequently, a 2.38% tetramethylammonium hydroxide solution was used, and after 1 minute of development under stirring at 2 3 t, it was washed with pure water and dried to form a photoresist pattern. The photoresist thus formed was evaluated in the following manner. (1) Sensitivity (L/S) Immediately after exposure of the photoresist film formed on the germanium wafer, PEB' is subsequently subjected to alkali development, water washing, and drying to form a photoresist pattern. At this time, the exposure amount of the line width of 1 5 Onm and the space pattern (1 L 1 S ) formed as a line width of 1 to 1 was taken as the optimum exposure amount, and the sensitivity was evaluated by the optimum exposure amount. (2) Resolution (L/S) For the line and space pattern (1L1S), the minimum line width (nm) of the line pattern for the optimum exposure amount is taken as the resolution. (3) Small surface unevenness: For the line size and space pattern (1 L 1 S ) of the design size of 150 nm, the cross-sectional dimension of the line pattern is determined by a scanning electron microscope, and the minimum size is Lin 'the largest size is Lout, and Lout-Lin) was evaluated as Ld by Ld's on the following basis.

Ld not reached Ο.ΟΙμηι: ◎

Ld is Ο.ΟΙμηι:〇 -51 - 200914994

Ld is larger than Ο.ΟΙμχη: x The evaluation results of the present examples have a sensitivity of 17.0 pC/cm2, a resolution of 80 nm, and a small surface unevenness of ◎. (Examples 9 to 14, Comparative Examples 1 to 3) The components shown in Table 1 were mixed in the amounts shown in Table 1 to obtain a homogeneous solution, and the same conditions as in Example 8 were carried out except that the conditions shown in Table 1 were carried out. The composition solution (sensitive radiation linear composition) was prepared. Subsequently, a photoresist pattern was formed from the adjusted _ ray composition, and the formed photoresist was subjected to various evaluations. The evaluation results are shown in Table 1. -52- 200914994 For small surface irregularities 1 ◎ ◎ ◎ ◎ ◎ 〇X Cannot form pattern X Resolution 90nm 80nm 90nm 90nm 80nm 90nm lOOnm 110nm Sensitivity (μ C/cm2) o (N os' o (N om (N pm ( N i〇>ri (N o vd (N ο PEB condition time (S) § § g § § temperature CC) 〇om § 〇cn r—* 〇〇ο ο PB condition time (S) § § § § § § § § Temperature CC) o O 〇cn 〇cn omoo ο ο Solvent m ^ ιϊιϊΒ oi〇O vn oo 〇wn oo ο Ό ο Type CN Q (NQ fN Q cn Q m QQ cn Q m ά rn Q _ a ru Λη en Φ ιΙΤΤΗ oso § o Ό oso Ό 〇o Ό ο ο § Type QQ ά QQQQ ά ά (c) Acid diffusion control agent _ A ru m Φ liiiH 1 1 1 1 1 1 1 I 1 Type 1 1 t 1 r 1 1 1 1 TTJ seven mi Φ mw liiiB o 〇Ov 〇o 〇o rn 〇cn ο rn Ο Category 1_ 1 u U ΓΛ ΰ 1 U ΰ <N u 3 3 ό mm 欢ββ黯v 〇\ o 〇\ 〇s ON o Os ΟΝ Ον Type cn ώ CN ώ 1 m ώ 1 DD ώ CQ CQ (a) Compound _ a ru rir> m. Φ 1111a OOOO o O 〇o ο ο ο Type 5 1 < CN &lt ; (N < ( N << rn <<<<<<> Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative Example 1 Comparative Example 2 Comparative Example 3 -53- 200914994 Further, Example 9 to 1 4 and the materials used in Comparative Examples 1 to 3 are as follows: (b) the sensitive radiation linear acid generator: B-1: triphenylsulfonium trifluoromethanesulfonate B-2: N-(trifluoromethanesulfonate Bisyloxy)bicyclo[2.2.1]hept-5-diluted 2,3-dicarboxyindoleimide (citrate diffusion control agent: C-1: tri-n-octylamine C-2: triphenylsulfonate Acid salt C-3 : N-tert-butoxycarbonyl dicyclohexylamine solvent: D - 1 : ethyl lactate D-2: propylene glycol monomethyl ether acetate is evident from Table 1, containing Example 3~ The linear composition of the sensitive radiation of Examples 8 to 14 of any of the compounds of 5, compared with Comparative Examples 1 to 3 of any of the resins containing Comparative Synthesis Example 1 and Comparative Synthesis Example 2 It is confirmed that the film can be formed into a chemically amplified positive type light which can be effectively induced by an electron beam or an extreme ultraviolet ray and which is excellent in minute surface unevenness, etching resistance, and sensitivity, and which can form a fine pattern with high precision and stability. Resistance film. [Industrial Applicability] -54- 200914994 When forming a pattern of the sensitive radiation linear composition of the present invention, not only the line and space patterns have excellent resolution, but also fine surface irregularities are excellent, so that it can be used to form fine lines with EB 'EUV and X-rays. pattern. Therefore, the radiation sensitive composition of the present invention is extremely useful as a chemically amplified photoresist for semiconductor device manufacturing which is further refined and expected in the future. -55 -

Claims (1)

200914994 X. Patent Application No. 1 · A sensitive radiation linear composition characterized by comprising U) a compound represented by the following general formula (1), and (b) a sensitive linear acid generated by irradiation of radiation to generate acid Agent (In the formula (1), R is each independently a hydrogen atom or a valence acid dissociable group, and R1 is independently a substituted or unsubstituted methyl group or a carbon number of 2 to 8 substituted or unsubstituted. An alkyl group, γ independently of each other, a substituted or unsubstituted alkyl group having a carbon number, a substituted or unsubstituted alkenyl group having a carbon number of 2 to 1 Å, or a substituted or unsubstituted carbon number of 2 to 10. An alkynyl group, a substituted or unsubstituted aryl fluorenyl group having a carbon number of from 1 to 1 Å, a substituted or unsubstituted alkoxy group having a carbon number of 10, or a substituted or unsubstituted phenoxy group, q is independent of each other. Or "0 2, such as the sensitive radiation linear composition of the patent range i-th item -56-, 卞200914994, the general formula (2) represents the combination of the above formula (1), Millennium, J The compound of Yiwu is the following: [Chemical 2] (In the formula (2), each of R is independently a hydrogen atom or a monovalent acid dissociable group, and r1 is independently a substituted or unsubstituted methyl group or a substituted or unsubstituted carbon number of 2 to 8. Alkyl). 3. The sensitive radiation wire composition of claim 2, wherein the compound represented by the above formula (2) is a compound represented by the following formula (3): -57- 200914994 (In the formula (3), R each independently represents a hydrogen atom or a monovalent acid dissociable group). 4. The radiation sensitive linear composition according to any one of claims 1 to 3, wherein the acid dissociable group is a group represented by the following formula (4 _ 1) or (4 - 2): 4] Ο R4 (4-1) (4-2) (In the formula (4-1), R2 is a linear or branched carbon having a carbon number of 1 to 40 which may be substituted or unsubstituted with a substituent which may contain a hetero atom. Or an alkyl group having a cyclic structure, η is an integer of 〇~3, and in the formula (4-2), R3 is a straight or unsubstituted carbon number of 1 to 40 which may be substituted with a hetero atom-containing substituent. Chain, branched or -58- 200914994 Acyclic alkyl group, R4 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). 5. The linear composition of the sensitive radiation according to item 4 of the patent application, wherein R2 in the above formula (4-1) is a third butyl group, a 2-methyl-2-adamantyl group, a 2-ethyl group- 2—adamantyl, 1-ethylcyclopentyl or 1-methylcyclopentyl, and η is 0 or 1, wherein R 3 in the above formula (4-2) is adamantyl and R 4 is a hydrogen atom, Or R4 is methyl and R3 is 2-methyl-2-adamantyl, or R4 is methyl and R3 is 2-ethyl-2-adamantyl. 6. The sensitive radiation linear composition of claim 5, wherein the (b) radiation sensitive metal generator is at least selected from the group consisting of a key salt, a diazomethane compound, and a sulfonimide compound. One. The sensitive radiation linear composition according to any one of claims 1 to 3, 5 and 6, which further comprises (c) an acid diffusion controlling agent. 8) The linear composition of the sensitive radiation as disclosed in claim 4, which in turn contains (c) an acid diffusion controlling agent. 9 · A compound represented by the following formula (1)' -59- 200914994 (In the formula (1), each R is independently a hydrogen atom or a monovalent acid dissociable group, and at least one of them is an acid dissociable group, and R1 is independently a substituted or unsubstituted methyl group or a carbon. Substituted or unsubstituted ketones of 2 to 8 are independently substituted or unsubstituted by the substituted or unsubstituted dibasic carbon of carbon (4) The number 2~1〇 of the substituted alkynyl group, the pulverization 7〗 annihilation - the carbon number 7~10 substituted or unsubstituted aryl carbon number 1~1 0 A w/top, anthracene or unsubstituted alkoxy group or a substituted phenoxy group 'q is independently of each other (4)). For the application of the compound of the ninth item of the Guangdong section, the system (2) means: 1々---60-200914994 (2) (In the formula (2), R is each independently a hydrogen atom or a monovalent acid dissociable group, and at least one of R is an acid dissociable group, and R1 is independently a substituted or unsubstituted methyl group. Or a substituted or unsubstituted alkylene group having a carbon number of 2 to 8. 1 1. The compound of the first paragraph of the patent application is expressed by the following general formula (3): -61 - 200914994 (In the formula (3), each of R is independently a hydrogen atom or a valence acid dissociable group, and at least one of R is an acid dissociable group). The compound according to claim 11 wherein the acid dissociable group is a group represented by the following formula (^) or (4_2): R4 (4_1) (4-2) (In the formula (4-1), R2 is a linear or branched form having 1 to 4 carbon atoms which are substituted or unsubstituted with a substituent which may contain a hetero atom. The alkyl group of the cyclic structure, η is an integer of 〇~3, and, in the formula (4_2), R3 is a carbon stomach 1~40 & substituted with or substituted with a hetero atom-containing substituent; An alkyl group in the form of a branched, branched or cyclic structure, wherein V is a hydrogen atom or an alkyl group of carbon m. -62- 200914994 succinctly, there is no simple: the number is the map of the map element: the table pattern represents the book without the generation \ the fixed one or two Γ ν / IV VIII. If there is a chemical formula in this case, please reveal the best display invention Characteristic chemical formula: (Y)q (1)