TW201131299A - Radiation-sensitive resin composition and novel compound - Google Patents

Abstract

Disclosed are: a radiation-sensitive resin composition which can response to (extreme) far ultraviolet rays such as a KrF excimer laser and an ArF excimer laser, X-rays such as a synchrotron radiation beam, and electron beams effectively to form a resist film which has good nanoedge roughness and on which a fine pattern can be formed stably with high precision; and others. The radiation-sensitive resin composition comprises an acid generating agent represented by formula (1-1), another specific compound, and a solvent. [In the formula (1-1), M+ represents a sulfonium cation represented by formula (2); and n represents an integer of 2 to 10.] [In formula (2), R1 to R3 independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, or at least any two of R1 to R3 are bound to each other to form a ring together with a sulfur atom contained in the formula.]

Description

201131299 VI. Description of the Invention: Technical Field of the Invention The present invention relates to a radiation sensitive linear resin composition and novels. In more detail, the present invention relates to being suitable for use by, for example, KrF, ArF excimer laser, F2. Sensitive resin compositions and novel compounds used in chemically amplified photoresists such as excimer lasers, EUVs, etc. (external lines, synchrotron radiation, etc., X-rays such as X-rays, electron beams, etc., and finely processed photoresists.) [Prior Art] In the past, The manufacturing process of a semiconductor device such as 1C or LSI is microfabricated by lithography using a photoresist composition. In recent years, the integrated circuit of the integrated circuit has been required to form an ultrafine pattern of a submicron domain. With this, it has been found that the g-line is directed toward the i-line, the KrF excimer laser light, and the tendency to be shorter than the short-wavelength of the sub-laser light. Further, at present, in addition to the alignment, the electron beam or the X-ray is also used. Or the development of EUV technology. Using EUV light lithography is positioned as the next generation or pattern formation technology, so high sensitivity and high resolution are expected. Especially, The round processing time is shortened and the high sensitivity is required. However, in the pursuit of EUV, the positive photoresist not only causes a decrease in resolution, but also causes a rough edge of the nanoparticle, so it is strongly desired to develop and satisfy these characteristics at the same time. Photoresist. Compound. Excimer thunderpole) In each of the ray-transfers of the far-purin beam, the lithography of the sub-generational photoresist with the ArF quasi-divided laser light with the domain or the quarter-wavelength is Very high sensitivity and deterioration, and the so-called -5 - 201131299 nano-edge roughness means that the interface between the pattern of the photoresist and the substrate is irregular due to the photoresist characteristics and is oriented perpendicular to the line direction. When the pattern is viewed from directly above, the deviation between the design size and the actual pattern size occurs. Since the deviation from the design size is caused by the etching step using the photoresist as a mask, the electrical characteristics are deteriorated, so that the yield is deteriorated. In particular, in the ultra-fine field of 32 nm or less which is suitable for EUV, the edge roughness of the nanometer becomes an extremely important improvement problem. High sensitivity and high resolution, good pattern shape and good nano-edge roughness are conflicting relationships. It is very important to satisfy these characteristics at the same time. A variety of reviews are conducted to satisfy both high sensitivity, high resolution, good pattern shape, and good nano edge roughness. For example, Patent Documents 1 to 4 disclose a radiation sensitive linear resin composition using a photoacid generator which produces two sulfonic acids in the same molecule. Further, Patent Document 5 discloses a sensitive radiation linear resin composition using two photoacid generators. Further, Patent Document 6 discloses a sensitized radiation linear resin composition using a photoacid generator which produces a strong acid and a photoacid generator which produces a weak acid, and Patent Document 7 discloses that a carboxylic acid is produced using a boiling point of 150 ° C or higher. A sensitive radiation linear resin composition of a compound and a compound which produces an acid other than a carboxylic acid. [Prior Art Document 1 [Patent Document] Patent Document 1: International Publication WO2004/1 0705 No. 1 Patent Document 2: Special Opening 2004-3 5 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei No. Hei No. 5 - 1 8 1 2 7 No. 9 Patent Publication No. JP-A No. 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 The linear radiation resin composition disclosed in ~7 still cannot satisfy high sensitivity, high resolution, good pattern shape and good nano edge roughness. The present invention has been developed in view of the problems of the prior art, and the object thereof is to provide an X-ray or an electron for a KrF excimer laser, an ArF excimer laser, an EUV, etc. The beam can be effectively sensed, and the nano-edge roughness is good, and at the same time, the sensitive radiation linear resin composition which can form a fine-grained chemically amplified positive-type resist film can be formed with high precision and stability, and can be suitably A novel compound is used as a linear acid generator for the radiation. [Means for Solving the Problem] As a result of a positive review of the above-mentioned problems, the inventors of the present invention have found that the subject can be achieved by a linear composition of a sensitive radiation containing a sensitive radiation linear acid generator having a specific structure. invention. The invention is as follows. [1] A radiation-sensitive linear resin composition comprising a sensitive radiation linear acid generator represented by the following formula (11-1), a compound represented by the following formula (X), and a solvent, 】* I MG [C01] Ο 〇

+ — / M OSf ιι V sigma-O Μ+ (1-1) Ο CF Ο [In the formula (1-1), M+ represents a phosphonium cation represented by the following formula (2), and two M + They may be the same or different from each other, η represents an integer of 2 to 10], [Chemical 2]* I MG [C02]

\ 2 R

R——S

3 R (2 [In the formula (2), R1, R2 and R3 independently of each other represent a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, or substituted or unsubstituted. An aryl group having 6 to 18 carbon atoms, or two or more of R1, R2 and R3 bonded to each other to form a ring together with a sulfur atom in the formula], [Chemical 3]* I MG [C03] R5 L γ- ( X) R6 R7 [In the general formula (X), R5, r6 and r7 independently of each other represent a substituted or unsubstituted linear or branched group of 1 to 1 fluorene or substituted or unsubstituted. The aryl group of 6 to 18 carbons or any two or more of R5, R6 and R7 are bonded to each other with a sulfur atom in the formula to form a ring 'Y' is a carboxylic acid anion -8- 201131299 sub] [2] A sensitive radiation linear resin composition characterized by containing a sensitive radiation linear acid generator represented by the following general formula (1-2) and a solvent, [Chemical 4]* I MG [C04] Μ _〇 -HcF2Vr°" (1-2) Table 2~1 0 integral [In the general formula (1-2), M + represents a cation with the following general formula (2-1-1), and two M + Same or different from each other, η represents the number], [Chemical 5]* IMG [C05]

[In the formula (2-1-1), each a independently represents an oxygen atom or a single bond, and each B independently represents a substituted or unsubstituted linear or branched group having 1 to 2 carbon atoms; a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 25 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and c, d and e each independently represent an integer of 〇~2 And (:, (at least one of 1 and e is 1 or 2). [3] A compound characterized by the following formula (ι_2) -9 - 201131299 [Chemical 6] * I MG [C06] + _ \ 9\ -M 〇-St〇F2-)^S-〇〇〇

M + [In the general formula (1_2), 'M+ is represented by the following formula (cations 'two M + may be the same or different from each other, number>, [Chemical 7]* I MG [C07] (1-2) -1 -1) indicates that the total value is 2 to 10

[In the general formula (2-1_1), each a represents independently an oxygen atom or a single bond, and each B independently represents a substituted or unsubstituted linear or branched alkyl group having a carbon number of 1-4 to 12; Or an unsubstituted alicyclic hydrocarbon group having 5 to 25 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and c, d and e are each independently an integer of 0 to 2, And at least one of c, d and e is 1 or 2]. [4] The compound according to the above [3], which is a radiation-sensitive linear acid generator. [Effect of the Invention] The sensitive radiation linear resin composition of the present invention can effectively induce X-rays such as KrF quasi & sub-laser, ArF excimer laser, EUV, etc., and -10-201131299 step radiation. The electron beam has excellent edge roughness, sensitivity and resolution, and can form a chemically amplified positive type resist film which can form a fine pattern with high precision and stability. The novel compound of the present invention can be used as a sensitive radiation linear acid generator in a sensitive radiation linear resin composition. [Embodiment] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. That is, those skilled in the art can make appropriate changes, improvements, etc. to the following embodiments without departing from the spirit and scope of the invention, and it is understood that these are included in the scope of the present invention. Further, "(meth) acrylate" in the present specification means "acrylic acid ester" or "methacrylic acid ester". [1] Sensitive Radiation Linear Resin Composition (I) The sensitive radiation linear resin composition of the present invention [hereinafter also referred to as "sensitive radiation linear resin composition (I)"] contains a specific sensitive radiation linear acid generator [hereinafter also It is called "acid generator (A 1 )"], other specific sensitive radiation linear acid generators (hereinafter also referred to as "acid generator (B)") and a solvent. By the sensitive radiation resin composition containing the acid generator (A1) and the acid generator (B), it is possible to form a photoresist film which has a low adverse effect on the environment or the human body and which can obtain a good pattern. -11 - 201131299 [1 -1 ] The radiation-sensitive linear acid generator (A1) The acid generator (A1) is represented by the following formula (1-1). Since the acid generator (A1) has a strong fluorine-containing electron-withdrawing group at the α-position of the sulfonyl group in its structure, a sulfonic acid having a high acidity is produced by exposure or the like (the following general formula ( La) indicates sulfonic acid). Further, the acid generator (A 1 ) has a high boiling point in addition to the function as a linear radiation acid generator, and is less volatile in the photolithography step, and shortens the acid diffusion distance in the photoresist film. That is, it has the characteristics that the diffusion length of the acid is appropriate. [化8]* I MG [C08] Ο 0 +M Ο-S—fcF2")~S~0 M+ ([I) μ ' '/gate η Ο 0 [in general formula (1-1), M + The cation is represented by the following formula (2), and two M + may be the same or different from each other, and η represents an integer of 2 to 10] [Chemical 9]* I MG [C09] R2

1 + / R - S

3 R (2 [In the formula (2), R1, R2 and R3 independently of each other represent a substituted or unsubstituted linear or branched alkyl group having 1 to 1 carbon number, or substituted or unsubstituted An aryl group having 6 to 18 carbon atoms, or two or more of R1, R2 and R3 bonded to each other to form a ring together with a sulfur atom in the formula], and η in the formula (1-1) is 2 to 10 The integer is preferably an integer of 2 to 6, more preferably 3 or 4. -12- 201131299 A linear or branched alkyl group having an unsubstituted carbon number iqo in R^R3 of the formula (2) Listed as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, isooctyl a base, a n-decyl group, a n-decyl group, a 2-ethylhexyl group, etc. Further, the alkyl group may also have a halogen atom such as fluorine, chlorine, bromine or iodine, a hydroxyl group, a mercapto group and a hetero atom (for example, a halogen atom, Substituted with a substituent such as an organic group such as an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a ruthenium atom, etc. The unsubstituted aryl group having 6 to 18 carbon atoms in RLR3 of the formula (2) is exemplified by, for example, benzene. Base, 1-naphthyl, 2- a group, a fluorenyl group, and a fluorene group, etc. Further, the aryl group may also have a halogen atom such as fluorine, chlorine, bromine or iodine, a thiol group, a sulfhydryl group, a fenthyl group, and a hetero atom (for example, a fang atom, oxygen). The substituent of the organic group or the like of the atom _ nitrogen atom, a sulfur atom, a phosphorus atom, a ruthenium atom or the like is substituted. The key cation represented by the formula (2) preferably has the following formula (2-1) or ( 2-2) The key cation represented by the ruthenium cation represented by the following general formula (2 -1 -1 ). -13- 201131299 [Chemical 1 Ο 】* I MG [CIO]

[In the formula (2-1), Ra, Rb and Re independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a substituted or unsubstituted linear or branched alkane having a carbon number of 1 to 12; a substituted, unsubstituted or substituted aryl group having 6 to 12 carbon atoms, -0S02-RfS or -302-118 group, or two or more of Ra, Rb and Re bonded to each other to form a ring, but Ra When Rb and Rb are present in plural, they may be the same or different, and Rf and Rg independently represent a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms, substituted or unsubstituted. An alicyclic hydrocarbon group having 5 to 25 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and q^q 3 independently of each other represents an integer of 0 to 5] [Expression (2-2) Wherein, Rd represents a hydrogen atom, a halogen atom, a hydroxyl group, a fluorenyl group, a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted carbon number of 6 to 8 The aryl group or two or more of Rd are bonded to each other to form a ring. However, when the plural of Rd exists, they may be the same or different. Re represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 7 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 7 carbon atoms, or two or more Re Bonding each other to form a ring, but, Re plural -14-201131299

[In the formula (2-1-!), each a independently represents an oxygen atom or a single bond, and each B independently represents a substituted or unsubstituted linear or branched alkyl group having 1 to 2 carbon atoms; , substituted or unsubstituted alicyclic hydrocarbon group having 5 to 25 carbon atoms, or substituted or unsubstituted aryl group having 6 to 12 carbon atoms, ^, d and e are mutually exclusive An integer, and at least one of c, d, and e is 1 or 2]. The linear or branched alkyl group having 1 to 12 carbon atoms which are unsubstituted in the general formula (2-1), Ra, and Rb, is exemplified by a methyl group, an ethyl group, a n-propyl group, an isopropyl group, or the like. n-Butyl, tert-butyl, n-pentyl, isopentyl n-hexyl, isohexyl, n-heptyl, n-octyl, isooctyl, n-decyl, n-decyl and 2-ethylhexyl. Further, the alkyl group may also be a halogen atom such as fluorine, chlorine, bromine or iodine, a thiol group, a sulfhydryl group or a hetero atom (for example, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a ruthenium atom). The substituent of the organic group or the like is substituted for the aryl group having an unsubstituted carbon number of 12 in Ra, Rb and v of the formula (2-1), for example, a phenyl group, a naphthyl group or the like. -15- 201131299 In addition, the aryl group may also be a halogen atom such as fluorine, chlorine, bromine or iodine, a hydroxyl group, a base group, and a hetero atom (for example, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom). Substituents such as an organic group such as an atom or a ruthenium atom are substituted. Formula (2-1). And the unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms in R6 is exemplified by, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, and n-pentyl group. Base, isopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, isooctyl, n-decyl, n-decyl and 2-ethylhexyl. Further, the alkyl group may be a halogen atom such as fluorine, chlorine, bromine or iodine, a hydroxyl group, a sulfhydryl group or a hetero atom (for example, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a ruthenium atom). The substituent of the organic group or the like is substituted for the unsubstituted alicyclic hydrocarbon group having 5 to 25 carbon atoms in Rf and Rg of the formula (2-1), and is exemplified by, for example, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a diamond. Alkyl group, raw borneol base, and the like. Further, the alicyclic hydrocarbon group may be a halogen atom such as fluorine, chlorine, bromine or iodine, a hydroxyl group, a sulfhydryl group or a hetero atom (for example, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a ruthenium atom). The substituent of the organic group or the like is substituted. The unsubstituted aryl group having 6 to 12 carbon atoms in Rf and Rg of the formula (2-1) is exemplified by a phenyl group, a naphthyl group and the like. Further, the aryl group may also be a halogen atom such as fluorine, chlorine, bromine or iodine, a hydroxyl group, a mercapto group, an alkyl group and a hetero atom (for example, a halogen atom, an oxygen atom, a -16-201131299 nitrogen atom, a sulfur atom, or a phosphorus atom). A substituent such as an organic group or the like of an atom, a sand atom or the like is substituted. The unsubstituted alkyl or linear alkyl group having 1 to 8 carbon atoms in the Rd of the formula (2-2) is exemplified by, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group or an n-butyl group. Tertiary butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, isooctyl and 2-ethylhexyl. In addition, the hospital base may also contain halogen atoms such as fluorine, chlorine, bromine, and iodine, a radical, a sulfhydryl group, and a hetero atom (for example, 'halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, ruthenium atom, etc.) The substituent of the organic group or the like is substituted for the unsubstituted aryl group having 6 to 8 carbon atoms in the Rd of the formula (2-2), for example, a phenyl group or the like. Further, the aryl group may also be a halogen atom such as fluorine, chlorine, bromine or iodine, a trans group, a mercapto group, an alkyl group and a hetero atom (for example, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom). Substituent substitution of an organic group or the like of an atom or the like. The linear or branched alkyl group of the unsubstituted carbon number of Re in the formula (2-2) is exemplified by, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, or a Tributyl, n-pentyl, isopentyl, n-hexyl, isohexyl and n-heptyl. Further, the alkyl group may also be a halogen atom such as fluorine, chlorine, bromine or iodine, a hydroxyl group, a mercapto group or a hetero atom (for example, 'halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, ortho atom, etc.). Substituent substitution of an organic group or the like -17- 201131299 The unsubstituted aryl group having 6 to 7 carbon atoms in Re of the formula (2-2) is exemplified by, for example, a phenyl group. Further, the aryl group may also be a halogen atom such as fluorine, chlorine, bromine or iodine, a hydroxyl group, a mercapto group, an alkyl group and a hetero atom (for example, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom). Substituted by a substituent such as an organic group. The unsubstituted alkyl or linear alkyl group having 1 to 12 carbon atoms in the formula (2-1-1) is exemplified by, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a n-butyl group. Base, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, isooctyl, n-decyl, n-decyl and 2-ethylhexyl. Further, the alkyl group may be a halogen atom such as fluorine, chlorine, bromine or iodine, a hydroxyl group, a sulfhydryl group or a hetero atom (for example, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a ruthenium atom). The substituent of the organic group or the like is substituted for the unsubstituted alicyclic hydrocarbon group having 5 to 25 carbon atoms in the formula (2-1-1), which is exemplified by, for example, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a diamond. Alkyl, borneol, and the like. Further, the alicyclic hydrocarbon group may also have a halogen atom such as fluorine, chlorine, bromine or iodine, a hydroxyl group, a sulfhydryl group and a hetero atom (for example, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a ruthenium atom, etc.) Substituted by a substituent such as an organic group. The unsubstituted aryl group having 6 to 12 carbon atoms in the formula (2-1-1) is exemplified by a phenyl group, a naphthyl group and the like. • 18- 201131299 Further, the aryl group may also be a halogen atom such as fluorine, chlorine, bromine or iodine, a 13⁄4 group, an alkyl group and a hetero atom (for example, a halogen atom, an oxygen atom, a sulfur atom, a phosphorus atom or a ruthenium atom). Substituted by an organic group or the like. These specific oxime cations represented by the general formula (2), (2-1), (2-2) or (2-1) may, for example, be substituted by the following formula (i-Ι) ~ (, a hydroxyl atom, -1 ) Table i-8 1 ) [Chemical 1 2 ] * I MG [C12]

(i-3) (i-6)

(i-9)

(i-1〇) C2H5

(i-12) -19- 201131299 【化1 3 】* I MG [C13]

(M5)

(i-18)

OCH2COOC(CH3)3

0 0 (i-20)

Y 〇-C{CH3)3 -20- (••23) 201131299 【化1 4 】* I MG [C14]

OC(CH3)3 (i-21)

OCH2COOC(CH3)3

0^0-C(Ch3)3 0

(H3C) 3CO

(H3C)3COOCH2CO

(i-25) fork (η3〇3〇-〇

-21 - 201131299 【化1 5 】* I MG [C15]

[化1 6 】* I MG [C16]

(1-35}

9 h3c-s+ (i-38) ch3

OH

H3c-s+ ch3 (i-39) ch3 H3C-S+ (i-40) CH3 ch2ci -22 201131299 【化1 7 】* I MG [C17] CH, h3c-s+- ch2ch2ch2ch3 /=\ (i^2) H3CH2CH2CH2C -S+- (i-43) o

OH

H3c-s+ ch3 (i-44)

OH

H3C-S+ OH ch3 (M5)

OH

OH H3C-f CH3 (i-46) 【化1 8 】* I MG [C18] 〇-〇

(i-47) HO (i-48)

H3CO HO H3CO

(i-49) h3ch2ch2ch2c HO h3ch2ch2ch2c

(i-5〇)

H3c HO H3C

H3C HO H3C

H, C

(i-52)

HO h3c'

H3c h3c h3c (i-53) 【化1 9 】* I MG [C19]

H3CH2CH2CH2CO

(H3C)2HC (i-54) H3CH2CH2CH2CO

o (i-55)

CijH25° 's〇 "Lang" H3CH2CH2CH2CO

(i-57) 〇 (i-58)

(i-59 ) -23- , 0 201131299 【化 2 Ο 】* I MG [C20]

Or

(i-60)

(i-62)

(i*63) 【化 2 1 】* I MG [C21]

-24- 201131299 【化2 2 】* I MG [C22]

25- 201131299 【化2 3 】* I MG [C23]

〇-h2c-|-〇-

P

(i-74) (i-75)

Among the phosphonium cations, the above formula (i-1), formula (i-2), formula (i-6), formula (i-8), formula (i-13), and formula (i-) are preferred. 19), Formula (i-25), Formula (i-27), Formula (i-29), Formula (i-33) ' Formula (i-64), Formula (i-65), Formula (i-66) ), formula (i-67), formula (i-68), formula (i-69), formula (i-70), formula (i-71), formula (i-72), formula -26-201131299 ( I-73) is preferably a cation of the above formula (N64), (i-65), (i-66), (i-67), (68), and C i - 6 9 ), the formula (i-70), the formula (1-71), the formula (i-72), the formula (Bu), the mirror cation. The sulfonic acid anion in the acid generator (A1) It can be produced according to the general method described in, for example, JP-A-7-507580. The M+ (germanium cation) in the acid generator (A1) can be based on, for example, Advances in Polymer Science, Vο 1. 62, Ρ·1 - 48 ( 1 984 ) * The general method described in JP-A-2005-1 (the publication No. 956, etc.). Further, the acid generator (A 1 ) contained in the sensitive radiation linear resin composition (I) of the present invention is — 锍 cation when exposed or heated (M +) dissociates to produce an acid. Specifically, a sulfonic acid represented by the following formula (la) is produced. [Chemical 2 4 ] * I MG [C24] 〇 \ II 4-S-OH , η丨丨〇 〇(1a) II / HO-S-rCFo II \ 〇 [in the formula (1), η is an integer of 2 to 10]. Further, the synthesis method of the acid generator (A 1 ) is not particularly limited. However, it can be synthesized, for example, by reacting a compound represented by the formula (Z) with a halide of a desired key cation (M+) (for example, Μ + Br') in an aqueous solution as shown in the following reaction formula. - 201131299 【化2 5 I * I MG [C25]

(Z) [in the formula (z), n is an integer of 2 to 10]. Further, the sensitive radiation linear resin composition (I) of the present invention may contain only one type of the above acid generator (A1), or may contain two or more types. The content of the acid generator (A1) in the radiation-sensitive linear resin composition (I) of the present invention is usually 0.1 to 50 parts by mass, preferably 1 to 4, based on 1 part by mass of the resin (C) described later. 〇 mass parts, more preferably 5 to 30 quality S parts. When the content of the acid generator (A 1 ) is less than 0.1 part by mass, it is difficult to sufficiently exhibit the desired effects of the present invention. On the other hand, when it exceeds 50 parts by mass, there is a drop in transparency, pattern shape, heat resistance, and the like of the radiation. [1-2] Compound (B) The above compound (B) is represented by the following formula (X). [Chemical 2 6 ]* I MG [C26] R5 L γ- (X) R6 R7 [In the formula (X), R5, R6 and R7 independently of each other represent a substituted or unsubstituted carbon number of 1 to 1 Å. a linear or branched alkyl group, or a substituted or unsubstituted aryl group having a carbon number of 6 to 18 or any two or more of R5, R6 and R7 bonded to each other to form a ring together with a sulfur atom in the formula 'For the carboxylic acid yin away • 28 · 201131299 child]. Needle # R5, R6 and R7 in the general formula (X) can be directly used for the description of R2 and R3, respectively. The specific phosphonium cation in R1 (X) in the above formula (2) can be exemplified by the above formula (i-1) - (1-81). Preferably, the formula (i-1), the formula (i-2), the formula (6), the formula (1-8), the formula (ί.13), the formula (i-19), and the formula (i- 25) Formula (1-27), Formula (i-29), Formula (i-33), Formula (i-64), Formula (1 65) Formula (1_66), Formula (i-67), Formula (i -68), formula (i-69) formula (1-70), formula (i-7 1 ), formula (i-72), formula (i-73), cations, mashing 隹The formula (1 - 6 4 ), the formula (1 - 6 5 ), the formula (i-68 ), the formula (i-69 ), the formula (i-72 ), and the formula (i_73) represent the Xiangyang type (i -66), formula (|_67) i-70), formula (i-71), formula ion. Further, Y- in formula (X) is a carboxylic acid anion, and r9co〇- represents R represents a substitution or Unsubstituted carbon number 12 linear or branched thiol, substituted or unsubstituted carbon number 丨~1 2 linear or branched decyloxy, substituted or unsubstituted An alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 22 carbon atoms; a linear or branched alkyl group having 1 to 12 carbon atoms in R and a carbon number 1 to 12 linear or branched j: the hydroxyl group may be substituted or unsubstituted Specific examples of the substituent substituent include, for example, a methyl group, an ethyl group, a propyl group, a hydroxyl group, a carboxyl group, a halogen atom (a fluorine atom, a bromine atom, etc.), an alkoxy group (methoxy group, an ethoxy group, a propoxy group, or the like). A linear or branched alkyl group having a carbon number of 1 to 1 2 in 9 is exemplified by, for example, -29-201131299 methyl group, ethyl group, n-propyl group, and isopropyl group. Base, n-butyl, 2-methylpropyl, 1·methylpropyl, tert-butyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, Perfluorooctyl, etc. Among these, methyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl is preferred, and trifluoromethyl is preferred. The carbon number in R9 is 1. The linear or branched alkoxy group of ~12 is exemplified by, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a 2-methylpropoxy group, a 1-methyl group. a propoxy group, a third butoxy group, etc. The alicyclic hydrocarbon group having 4 to 20 carbon atoms in R9 may be substituted or unsubstituted. Specific examples of the substituent are exemplified by methyl group, B, for example. Base, propyl, hydroxyl, carboxyl, halogen An atom (a fluorine atom, a bromine atom, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), an alkyloxycarbonyl group, etc. an alicyclic ring having a carbon number of 4 to 20 in R9 Specific examples of the hydrocarbon group are, for example, a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, a cyclooctyl group, a cyclodecyl group or a cyclododecyl group; an adamantyl group, a proadamantyl group, or a decahydronaphthalene residue. (decalinyl), tricyclodecyl, tetracyclododecyl, borneol, cedrol, and the like. The aryl group having 6 to 22 carbon atoms in R9 may be substituted or unsubstituted. Specific examples of the substituent are, for example, a methyl group, an ethyl group, a propyl group, a hydroxyl group, a carboxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy group (methoxy group, ethoxy group, or propoxy group). , butoxy group, etc.), alkyloxycarbonyl group, and the like. The aryl group having 6 to 22 carbon atoms in R9 may be exemplified by a structure derived from the following (X-1) -30 to 201131299 to (x-3). Further, when R9 is a group derived from (x-2) below (that is, a naphthyl group), the bonding position of a carbon atom bonded to a COCT portion in R9coct may be either one or two. At the office. Further, when R9 is a group derived from (x-3) described below (that is, a sulfhydryl group), the bonding position of the carbon atom bonded to the COCT portion in R9COO_ may be 1 position '2 position and 9 position Anywhere. [Chem. 2 7] 氺I MG [C27] 0 (X-3) (X-1) (X-2) As for these Y·, it is preferable to use CH3COCT, the following formula (3-l)~ (3) -5 ) represents a carboxylic acid anion. [化 2 8 】* I MG [C28]

^^^COO' (3-1) (3-2) COO'

F3C\^%^〇H coo" (3-4) (3-5) The compound (B) can be produced by a general method described in, for example, JP-A-i 2 5 907. Further, the sensitive radiation linear resin composition (I) of the present invention may contain only -31 - 201131299 one of the above compounds (B), and may contain two or more kinds. The content of the compound (B) in the sensitive radiation linear resin composition (I) of the present invention can be appropriately adjusted depending on the type or content of the acid generator (A1) and other acid generators to be described later, but with respect to 100 mass. The resin (C) to be described later is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, more preferably 5 to 20 parts by mass. When the content of the compound (B) is less than 0.1 part by mass, There is a difficulty in fully exhibiting the desired effects of the present invention. On the other hand, when it exceeds 30 parts by mass, there is a drop in transparency, pattern shape, heat resistance, and the like of the radiation. [1-3] Resin (C) The sensitive radiation linear resin composition (I) of the present invention contains an alkali-insoluble or alkali-insoluble resin containing a repeating unit having an acid-dissociable group (hereinafter also referred to as "resin (C)" ). The resin (C) is a resin which becomes alkali-soluble by the action of an acid. Here, the term "alkali-insoluble or alkali-insoluble" means the alkali-developing condition used in forming a photoresist pattern from a photoresist film formed using a linear radiation-sensitive resin composition containing a resin (C). When the film of the film thickness of 100 μm of the resin (C) is used instead of the photoresist film, the initial film thickness of the film remains 50% or more after development. Since the sensitive radiation linear resin composition (1) of the present invention contains the resin (C), it can effectively induce electron beams or extreme ultraviolet rays in the lithography process, and can form a film with high precision and stability. A chemically amplified positive resist film of the pattern. -32- 201131299 The repeating unit having an acid dissociable group contained in the resin (C) is an acid dissociable group dissociated by the action of an acid. The repeating unit is not particularly limited as long as it has the above-described effects, but is preferably a repeating unit represented by the following general formula (P -1 ) (hereinafter referred to as "repeating unit (P·1)") and has the following general formula (P-2) At least one of the repeating units (hereinafter referred to as "repetitive units (p-2)"). By using at least one of the repeating units (P-1) and (P-2) as the repeating unit having the acid dissociable group, the advantage of obtaining good sensitivity is obtained. [化 2 9 ]* I MG [C29]

(P-1) r22-c-r22

I R22 [In the formula (P-I), R21 represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and R22 independently represents a linear or branched alkyl group having a carbon number of 1 to 4, and a carbon number. An aryl group of 6 to 22, or a carbon number of 4 to 2 fluorene or a group derived from the same, or any two of R22 bonded to each other, together with each bonded carbon atom to form a divalent group An alicyclic hydrocarbon group or a group derived therefrom, the remaining one R22 represents a linear or branched alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 22 carbon atoms, or a carbon number of 4 to 20 An alicyclic hydrocarbon group or a group derived therefrom. -33- 201131299 【化3 Ο 】* I MG [C30]

(P-2) [In the formula (P-2), R23 represents a hydrogen atom, a methyl group, a methyl group, and R24 independently represents a linear group having a carbon number of 1 to 4 or a carbon number of 4 to 20; The alicyclic hydrocarbon group may be bonded to each other by the or two R24 groups, and the divalent alicyclic hydrocarbon group bonded to each carbon or a group derived therefrom, and the remaining I represents a linear chain having a carbon number of 1 to 4. a branched or branched alkyl group, or a carbon number alicyclic hydrocarbon group or a group derived therefrom. The alkyl group having 1 to 4 carbon atoms in R22 of the above formula (P-1) is exemplified by, for example, a methyl group, an ethyl group, a n-propyl group, a group, a 2-methylpropyl group, a 1-methylpropyl group, One of the carbon numbers 4 to 20 in R22 of the formula (P-1) such as the third butyl group is exemplified by, for example, derived from norbornane, tricyclodecane, tetracyclohexane or cyclobutane, cyclopentane, A group composed of an alicyclic ring such as cyclohexane, cycloheptane or alkane. Further, the group derived from the alicyclic hydrocarbon group is exemplified by a cyclic hydrocarbon group such as methyl group, ethyl 'n-propyl group, isopropyl 2-methylpropyl group, 1-methylpropyl group, tert-butyl group, or the like. One or more or more carbon atoms, branched or cyclic alkyl groups: a R24 formed by a trifluoromethyl group or a hydroxyl group or a branched alkane derived from a base atom, and a linear chain of one of 4 to 20 Or a isopropyl group, a n-butyl group, a valence alicyclic hydrocarbon cyclododecane, a gold octane or the like, the above-mentioned one-valent aliphatic group, n-butyl group, linear group of 1 to 4, etc. . -34- 201131299 The aryl group having 6 to 2 carbon atoms in R2 2 of the formula (P-1) is exemplified by a structure derived from the following structures (y-Ι) to (y-3). Further, when R22 is a group derived from (y-2) below (that is, a naphthyl group), a carbon atom (bond) bonded to a [-〇-C(R22)3] moiety of the above formula () The bonding position of the carbon atom bonded to the oxygen atom may be any one of the 1st position and the 2nd position. Further, when R22 is a group derived from (y-3) below (that is, a fluorenyl group), the carbon atom bonded to the [-0-C(R22)3] moiety of the above formula (P-1) The bonding position can be any of t, 2, and 9 positions. Further, the aryl group may also be substituted. Specific examples of the substituent are exemplified by methyl 'ethyl, hydroxy 'carboxy' halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group). Alkyloxycarbonyl, and the like.

Further, the divalent alicyclic hydrocarbon group in which two R22 are bonded to each other and each of the bonded carbon atoms (carbon atoms bonded to the oxygen atom) is exemplified as a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. Wait. Specifically, it is exemplified by a group composed of an alicyclic ring derived from, for example, norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane or cyclohexane. Further, the divalent alicyclic hydrocarbon group-derived group formed by bonding R22 to each other is exemplified by the above-mentioned divalent alicyclic hydrocarbon group via, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2- One or more of linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms such as methylpropyl group, 1-methylpropyl group and t-butyl group, or a group of -35 to 201131299 or more substituted groups. The repeating unit (P-1) is preferably a repeating unit represented by the following formula (P-1-1) to (P-1-7), more preferably a formula (P-1-2) , (p-1-3) or (p-1-4) indicates the repeating unit. When the resin (C) contains these repeating units, it can form a photoresist pattern having a superior edge roughness. [化 3 2 ]* I MG [C32]

(p-1-5) (p-1-6) (P-1-7) [In the formula (P-1-1) to (P-1-7), R21 represents a hydrogen atom, a methyl group, or a trisium group. Fluoromethyl or hydroxymethyl, R2 5 independently of each other represents a linear or branched alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 22 carbon atoms. In the R25 of the formula (P-1-1)~(P-1-7), the "carbon number 4 straight-36-201131299 chain or branched alkyl group" and the "aryl group 6 to 22 aryl group" The description of "linear or branched alkyl group having 1 to 4 carbon atoms" and "aryl group having 6 to 22 carbon atoms" in R22 of the above formula (P-1) can be used as it is. Further, the resin (c) may contain only one repeating unit (p-ι) or may contain two or more kinds. Further, the "linear or branched alkyl group having 1 to 4 carbon atoms" and the "valent alicyclic hydrocarbon group having 4 to 20 carbon atoms" in R24 of the above formula (P-2) are derived from or derived from The "base" and "any two R24 are bonded to each other to form a divalent alicyclic hydrocarbon group or a group derived therefrom" can be directly used as the R22 of the above formula (P-1). Among the "linear or branched alkyl groups having a carbon number of 1 to 4", "a carbon number of 4 to 20, a alicyclic alicyclic hydrocarbon group or a group derived therefrom" and "any two R22 are bonded to each other" The description of each of the bonded carbon atoms to form a divalent alicyclic hydrocarbon group or a group derived therefrom. In the repeating unit (P-2), a repeating unit represented by the following formula (p_2_n) is preferred. When the resin contains the repeating units, a photoresist pattern having a superior nanoedge roughness can be formed. -37- 201131299 [化3 3 】* I MG [C33] R23

R26 (P-2-1) [In the formula (P-2-1), R23 represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and R26 independently represents a linear chain having a carbon number of 1 to 4. Or branched alkyl]. The "linear or branched alkyl group having 1 to 4 carbon atoms" in R26 of the formula (P-2-1) can be directly used as the "carbon number 1 to 4" in R22 of the above formula (P-1). Description of a linear or branched alkyl group. Further, the resin (C) may contain only one repeating unit (P-2)' or may contain two or more kinds. Further, the resin (C) in the present invention preferably contains a repeating unit represented by the following general formula (C-1) to (C-4) in addition to the above repeating units (p-1) and (P-2). At least one of them. -38- 201131299

(〇H)k (R12), [In the formula (c-1), 'Ru represents a hydrogen atom or a methyl group, and r12 represents a hydrogen atom, a linear or branched alkyl group having a carbon number of 1 to 12, or a carbon number. A linear or branched alkoxy group, and k and 1 independently represent an integer of 〇~3 (however, satisfy k +1 $ 5 )]. [化 3 5 ]* I MG [C35]

(〇H)n (R14)m [In the formula (c-2), R13 represents a hydrogen atom or a methyl group, and R14 represents a hydrogen atom, a linear or branched alkyl group having a carbon number of 1 to 12, or a carbon number. The linear or branched alkoxy groups 'm and η of 1 to 12' independently represent an integer of 〇~3 (but 'satisfies m + nS5)). -39- 201131299 【化3 6 】* I MG [C36]

R15 f?-therapy =〇 NH

[In the formula (c-3), R15 represents a hydrogen atom or a methyl group, R1, a linear or branched alkyl group having 1 to 12 carbon atoms, or a carbon number or branched alkoxy group, and p and q are mutually Independently represents 0~, satisfying p + q S 5 )]. (c-4) [In the formula (c-4), R17 represents a hydrogen atom or a methyl group, R1, a linear or branched alkyl group having 1 to 12 carbon atoms, or a carbon number or branched alkoxy group. , r and s are mutually independent, and 树脂~3 The resin (C) in the present invention contains a formula (c-1: unit (hereinafter referred to as a repeating unit (c-1)), and is excellent in roughness. The resistive pattern. The straight alkyl group having a carbon number of 1 to 12 in R12 of the formula (c-1) is exemplified by, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group - 40 - a non-nitrogen atom 1 to 12 The linear integer (but [3 3 ]* I MG [C37]

1 represents an integer of a linear chain of hydrogen atoms 1 to 12. The table is not repeated; the edge of the nano-I or branched g, n-butyl, 201131299 2-methylpropyl, 1-methylpropyl, tert-butyl and the like. In order to make the nano edge roughness excellent, it is preferably a linear chain of carbon numbers i to 12 in R12 of a methyl group, an ethyl group, an n-butyl group or a tbutyl group of the formula (C-1). Or a branched alkoxy group is exemplified by, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a 2-methylpropoxy group, _Methylpropoxy, tert-butoxy and the like. Among these, 'the methoxy 'ethoxy group is preferred in order to make the nano edge roughness excellent. k in the formula (c-1) is an integer of 〇~3, preferably 1 or 2. Further, 1 is an integer of 〇~3, preferably an integer of 〇~2. The repeating unit (c-1) is specifically listed as a repeating unit represented by the following formulas (c-1 - 1) to (c-1-4). Further, the repeating unit (c-1) may be contained in the resin (C) alone or in combination of two or more. [化 3 8 ]* I MG [C38]

OH (c-1 -1) (c-1 -2) (c-1-3) (c-1-4) The repeating unit (c -1 ) can be used as a monomer by using the corresponding hydroxystyrene derivative And get. Further, by hydrolysis, it is also possible to obtain a compound obtained by using a hydroxystyrene derivative as a monomer. The monomer used to form the repeating unit (c - 1 ) is exemplified by, for example, p-41-201131299 ethoxylated styrene, p-(1-ethoxy)styrene, p-isopropenylphenol or the like. Further, when p-acetoxystyrene is used, a side chain hydrolysis reaction is carried out after the polymerization reaction to form a repeating unit (c-1). When the resin (C) in the present invention contains a repeating unit represented by the formula (C-2) (hereinafter referred to as "repeating unit (c-2)"), it can form a photoresist having superior nano edge roughness. Graphic type. The linear or branched alkyl group having 1 to 12 carbon atoms and the linear or branched alkoxy group having 1 to 12 carbon atoms in R14 of the formula (c-2) can be respectively exemplified as the above formula (c-1) A linear or branched alkyl group having 1 to 12 carbon atoms in R12, and a linear or branched alkoxy group having 1 to 12 carbon atoms in the same formula (c-2) m is an integer of 0 to 3, preferably 0 or 1. Further, η is an integer of 0 to 3, preferably 1 or 2. The repeating unit (c-2) is specifically listed as a repeating unit represented by the following formula (c-2-l) or (c-2-2). Further, the repeating unit (c-2) may be contained in the resin (C) alone or in combination of two or more. [化3 9 ]* I MG [C39] / H2 H , H2 CH3 ten c -c-) - ten c -c-) - =0 1=0 o o

OH OH (c-2-2) (c-2-1) -42- 201131299 The repeating unit (c-2) can be obtained by using the corresponding monomer. The monomer used to form the repeating unit (c-2) is exemplified by, for example, 4-hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, and the like. When the resin (C) in the present invention contains a repeating unit represented by the formula (c-3) (hereinafter referred to as "repeating unit (c-3)"), a photoresist pattern which is excellent in nanoedge edge roughness can be formed. type. The linear or branched alkyl group having a carbon number of 1 M 2 and the linear or branched alkoxy group having a carbon number of 1 to 12 in Ri6 of the formula (c-3) can be respectively exemplified as the above formula (c) -1) A linear or branched alkyl group having a carbon number of ι 12 in R12 and a linear or branched alkoxy group having a carbon number of 1 to 12 are the same in the formula (C-3) P is an integer of 〇~3, preferably 1 or 2. Further, q is an integer of 〇~3, preferably 〇 or 1. The repeating unit (c-3) is specifically exemplified by a repeating unit represented by the following formula (c_3_n or (c-3-2), etc. Further, the 'repeating unit (c-3) may contain only - in the resin (c) - Species may also contain two or more types.

(c-3-1) (c-3-2) -43- 201131299 The repeating unit (c-3) can be obtained by using the corresponding monomer. The monomer for producing the repeating unit (c-3) is exemplified by N-(4-hydroxyphenyl) acrylamide, N-(4-hydroxyphenyl)methacrylamide or the like. When the resin (C) in the present invention contains a repeating unit represented by the formula (c-4) (hereinafter referred to as "repeating unit (c-4)"), it is possible to form a photoresist pattern having superior nano edge roughness. type. The linear or branched alkyl group having 1 to 12 carbon atoms and the linear or branched alkoxy group having 1 to 12 carbon atoms in R18 of the formula (c-4) can be respectively exemplified as the above formula (c-1) A linear or branched alkyl group having 1 to 12 carbon atoms in R12, and a linear or branched alkoxy group having 1 to 12 carbon atoms are the same as the formula (c-4) Where r is an integer of 0 to 3, preferably 1 or 2. Further, s is an integer of 0 to 3, preferably 0 or 1. The repeating unit (c-4) is specifically exemplified by a repeating unit represented by the following formula (c-4-l) or (c-4_2). Further, the repeating unit (c-4) may be contained in the resin (C) alone or in combination of two or more. -44- 201131299

(c-4-1) (c-4-2) The repeating unit (c-4) can be used to form the monomeric acrylic acid 5-hydroxynaphthalene for the repeating unit (c-4) by using the corresponding single bone. -1-yl ester, 5-hydroxyl acrylate, and resin (C) may be further substituted with an acid-dissociating compound in addition to the above repeating unit (p-ι) repeating units (c -1 ) to (c - 4 ) [not A repeating unit (hereinafter referred to as c-5) of a compound containing a dissociable group by an action of an acid). The resin (C) in the present invention contains a repeating unit (a resist pattern which is more excellent in edge roughness of the nanometer. The non-acid dissociation used to form the repeating unit (c-5) is, for example, styrene, α-methyl a compound represented by styrene, 4-methylstyrene, 3-methylstyrene, isobornyl acrylate, acid tricyclodecyl ester '(meth)acrylic acid tetracycline (c-5-l) In the above, f-methylstyrene, 4-methylstyrene, 2-methylacetophenene, tricyclodecyl acrylate, and the following formula (c-5-1) are preferably obtained. For example, it is a methyl-1-yl ester, etc., (P-2) and a step derived from a non-isolated group (the acid form "repeating unit (:-5), the formable compound is listed as ethylene, 2-A a compound represented by a (meth) propylene acrylate, a styrene of the following formula i, a fluorene:-, or a 3-methyl benzene-45-201131299 Further, the repeating unit (c-5) may be only used in the resin (C) Containing one 'may also contain two or more. [Chemical 4 2 ] * I MG [C42] /CH3 H2〇=C,

The content ratio of the repeating unit having an acid-dissociable group in the resin (C) [in particular, the total content of the repeating units (p-1) and (p-2)]] is the total repeating unit contained in the resin (C) When the total amount is 100 mol%, it is preferably 1 mol% or more, more preferably 2 0 to 70 mol%, and still more preferably 2 0 to 60 mol%. When the content ratio is less than 1 mol%, the edge roughness of the nanoparticle deteriorates. Further, when the content ratio is 1 mol% or more (especially 20 to 70 mol%), a photoresist film exhibiting excellent nano edge roughness can be formed. The total content of the repeating units (ci) to (c_4) in the resin (C) is preferably 95% by mole or less, based on the total of all the repeating units contained in the resin (C), preferably 95% by mole or less. More preferably 1 to 95 mol% 'more preferably 10 to 95 mol%, preferably 4 to 80 mol%. When the content exceeds 95% by mole, the edge roughness of the nanoparticle deteriorates. Further, when the content ratio is 1 mol% or more, a photoresist film having more excellent edge roughness can be formed. -46 - 201131299 The total of the repeating units (p-:!), (p-2), and (cl) to (C-4) in the resin (C), the total repeating unit contained in the resin (C) When the total is 100% by mole, it is preferably 10% by mole or more, more preferably 40% to 1% by mole, and even more preferably 50% to 100% by mole. When the content ratio is less than 1% by mole, the edge roughness of the nanoparticle deteriorates. Further, when the content ratio is 〇 mol% or more, a photoresist film which exhibits excellent nano edge roughness can be formed. When the ratio of the repeating unit (c-5) in the resin (C) is 1% by mole based on the total of all the repeating units contained in the resin (C), it is preferably 60% by mole or less. Good for 〇~5 0 mol%. When the content ratio exceeds 60 mol%, the edge roughness of the nanoparticle deteriorates. Further, when the content ratio is 60% by mole or less, a photoresist film excellent in performance balance between resolution and nano edge roughness can be formed. The synthesis method of the above resin (C) is not particularly limited and can be obtained by, for example, conventional radical polymerization or anionic polymerization. Further, the phenol moiety or the naphthol moiety of the side chain in the above repeating units (c-1) to (c-4) can be subjected to acetamidine in the presence of a base or an acid by causing the obtained resin (C) in an organic solvent. Obtained by hydrolysis of an oxy group or the like. The above-mentioned radical polymerization can be used to generate at least one of the above repeating units (P-1) and (p-2) by, for example, in a nitrogen atmosphere, in the presence of a radical polymerization initiator in a suitable organic solvent. The monomer and, if necessary, the monomer for generating the above repeating units (c-1) to (c-5) are stirred and heated. The radical polymerization initiator is exemplified by, for example, 2,2,-azobisisobutyronitrile, -47-201131299 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2' -azobis-(yl-2,4-dimethylvaleronitrile), 2,2'-azobismethylbutyronitrile, 2,:dicyclohexylenitrile, mercaptomethylethylazomethamine , 2,2'-azobisdimethylpropionic acid methyl ester), 2,2'-azobisaryl pivalic acid, etc. azo: benzoyl peroxide, lauryl peroxide, 1 , an organic peroxide such as 1'-bis-butylperoxy)cyclohexane or 3,5,5-trimethylhexyldecylperoxyperoxy-2-ethylhexanoate; Waiting. Further, a polymerization aid such as 2,2,6,6-tetramethyl-yloxy, iodine or a thiol 'styrene dimer may be added as needed during the polymerization. The reaction temperature of the radical polymerization is not particularly limited and may be appropriately selected depending on the type and the like, and may be, for example, 50 to 200 °C. In particular, in the case of a nitrogen-based initiator or a peroxide-based initiator, it is preferred to set the initial life to a temperature of about 10 minutes to 30 hours, more preferably to have a half-life of about 30 minutes to 10 hours. . Further, the reaction time varies depending on the type of the initiator or the reaction temperature, but is preferably 50% or more of the reaction time of the initiator, and is about 0.5 to 24 hours under normal conditions. The foregoing anionic polymerization can be carried out by, for example, obtaining a monomer of at least one of the above positions (P-1) and (P-2) in the presence of an anionic polymerization initiator in an organic solvent under a nitrogen atmosphere, and The monomer of the above repeating units (c-1) to (c-5) is stirred and carried out at a predetermined temperature. The anionic polymerization initiators are exemplified by, for example, n-butyllithium, a second 4-methoxyazo (2,4-compound (third compound, hydrogen peroxide. 1-piperidine initiator) using a half initiator Different agents, most of the appropriate repetitive singles are maintained in butyl lithium-48- 201131299, tert-butyl lithium, ethyl lithium, ethyl sodium, 1,1-diphenylhexyl lithium, 1,1- An organic alkali metal such as diphenyl-3-methylpentyllithium. The reaction temperature of the anionic polymerization is not particularly limited, and may be appropriately selected depending on the type of the initiator, etc. In particular, when an alkyllithium is used as a starter, Preferably, it is -100 to 50. (:, more preferably -78 to 30. (:. In addition, the reaction time varies depending on the type of the initiator or the reaction temperature, but it is preferred that the initiator consumes 50% or more. The reaction time is, in most cases, about 0.5 to 24 hours. In the synthesis of the resin (C), the polymerization initiator may be used without heating, or the polymerization may be carried out by heating, or cationic polymerization may also be employed. Further, 'the side of the above repeating unit (c-1) ~ (C-4) is introduced by hydrolyzing the side chain of the resin (C) When the phenol moiety or the naphthalene moiety of the chain is used, the acid which can be used in the hydrolysis reaction is exemplified by p-toluenesulfonic acid and its hydrate, methanesulfonic acid, trifluoromethanesulfonic acid, malonic acid, oxalic acid, and I'l'. l-Organic acid such as trifluoroacetic acid; inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid or hydrogen bromide; pyridinium iron-toluenesulfonate, ammonium p-toluenesulfonate, 4-methylpyridyl-p-toluenesulfonic acid Salt salt, etc. In addition, the enumeration is inorganic test such as potassium hydroxide, sodium cyanide, sodium carbonate, and cesium carbonate; triethylamine, N-methyl-2-pyrrolidinone, piperidine, tetramethyl hydroxide An organic base such as ammonium or the like. The organic solvent used in the hydrolysis or hydrolysis is exemplified by a ketone such as acetone, methyl ethyl ketone or methyl amyl ketone; an ether such as diethyl ether or tetrahydrofuran (THF); Alcohols such as propanol; aliphatic hydrocarbons such as hexane, heptane, and Xinyuan; aromatic hydrocarbons such as benzene, toluene, and xylene; chloro-49-201131299 imitation, bromoform, dichloromethane, dibromomethane, Halogenated alkane such as carbon tetrachloride; ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether, An ester such as diol monomethyl ether acetate or cellosolve; an aprotic polar solvent such as dimethylformamide, dimethyl hydrazine or hexamethylsulfonamide. Acetone, methyl amyl ketone, methyl ethyl ketone, tetrahydrofuran, methanol 'ethanol, propanol, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate Preferably, the weight average molecular weight (hereinafter also referred to as "Mw") of the resin (C) measured by gel permeation chromatography (GPC) is preferably from 2,000 to 10,000, more preferably from 2000 to 1.00. 40000, and better for 2000~25000. Further, the ratio (Mw/Mn) of the Mw of the resin (c) to the number average molecular fi (hereinafter also referred to as "Μη") measured by GPC is preferably from 1 to 5, more preferably 1 to 1. 3. It is better for 1~2.5. Further, the radiation sensitive linear resin composition (I) of the present invention may contain only one kind of the above resin (C), or may contain two or more kinds. Π-4] Acid Diffusion Control Agent (D) The sensitive radiation linear resin composition (I) of the present invention is preferably additional in addition to the above-mentioned acid generator (A), acid generator (B), and resin (C). Containing an acid diffusion controlling agent (hereinafter also referred to as "acid diffusion controlling agent (D) J ) ° The acid diffusion controlling agent (D) is controlled to be produced by exposure from an acid generator (A) or an acid generator (B) The acid diffuses in the photoresist film, and suppresses the adverse chemical reaction in the unexposed region. By containing the acid diffusion controlling agent (D), the resulting linear composition of the sensitive radiation can be improved. The storage stability of the material further improves the resolution of the formed photoresist film, and at the same time suppresses the line of the photoresist pattern caused by the change of the standing time (PED) from the post-exposure to the post-exposure heat treatment. The sensitized radiation linear resin composition which is excellent in process stability is obtained. The acid diffusion controlling agent (D) is exemplified by, for example, a nitrogen-containing organic compound or a photosensitive basic compound. The above-mentioned nitrogen-containing organic compound is exemplified by, for example, the following through (4) a compound (hereinafter referred to as "nitrogen-containing compound (i)"), a compound having two nitrogen atoms in the same molecule (hereinafter referred to as "nitrogen-containing compound (ii)"), and having three or more nitrogen atoms The polyamine-based compound or polymer (hereinafter referred to as "nitrogen-containing compound (iii)"), a guanamine-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, or the like. [Chemical 4 3 ]* 1 MG [C43] R41 R41——N-R41 (4) In the formula (4), each R41 independently represents a hydrogen atom, a linear, branched or cyclic alkane which may be substituted a aryl group which may be substituted, or an aralkyl group which may be substituted. The alkyl group in R41 of the formula (4) is exemplified by a linear or branched alkyl group having 1 to 3 carbon atoms and a cyclic alkyl group having 3 to 30 carbon atoms. Specifically, the column -51 - 201131299 is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, cyclopropyl Base, cyclopentyl, cyclohexyl, adamantyl, raw borneol, and the like. The aryl group in R41 of the formula (4) is exemplified by an aryl group having 6 to 14 carbon atoms or the like. Specific examples thereof include a phenyl group, a tolyl group, a naphthyl group and the like. The aralkyl group in R41 of the formula (4) is exemplified by an aralkyl group having 6 to 12 carbon atoms. Specific examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and the like. Further, the above alkyl group, aryl group and aralkyl group may also be substituted. Specific substituents are exemplified by, for example, a methyl group, an ethyl group, a propyl group, a n-butyl group, a tert-butyl group, a hydroxyl group, a carboxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy group (methoxy group). , ethoxy, propoxy, butoxy, etc.). The nitrogen-containing compound (i) is exemplified by, for example, mono(cyclo)alkylamines, di(cyclo)alkylamines, substituted alkylamines, and aromatic amines. The nitrogen-containing compound (Π) is exemplified by, for example, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-di Aminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2- Bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 1,4-bis[1-(4-aminophenyl) -1-methylethyl]benzene, 1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene, bis(2-dimethylaminoethyl)ether, double (2-diethylaminoethyl)ether, 1-(2-hydroxyethyl)-2-imidinone, 2-hydroxyquinoxaline, N,N,N',N,-肆(2- Hydroxypropyl) ethylenediamine and the like. The nitrogen-containing compound (iii) is exemplified by, for example, a polymer of a polyethylenimine, a polypropyl-52-201131299-amine, a 2-dimethylaminoethyl acrylamide, or the like. The compound containing a guanamine group is exemplified by, for example, an amine compound containing an N-carbonyl group, and formamide, N-methylformamide methylformamide, acetamide 'N-methylacetamide, hydrazine. , dimethyl dimethyl ketone, propyl decylamine, benzamide, snail ketone, fluorene - methyl hydrazine, decyl sulphate - oxamantylamine, isocyanuric acid (2-hydroxyethyl) urea The compound is exemplified by, for example, urea, methyl urea, 1,1 -di1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylureidourea or the like. The nitrogen-containing heterocyclic compound is preferably, for example, an imidazole, a pyridinium, and a pyrazine, a pyrazole, a pyridazine, a quinoxaline, an anthracene, an ophthalmidine, a piperidine ethanol, and a 3-piperidinyl-I,2- Propylene glycol, morpholine, 4-methyl-1-(4-morpholinyl)ethanol, 4-ethylmercaptomorpholine, 3-( Ν-η, Ι I, 2-propanediol, I,4-dimethylpiperazine , I, 4-diazabicyclo[2, etc. Further, the acid diffusion controlling agents (D) may be used alone or in combination of two or more. The acid diffusion controlling agent (D) is present in an amount relative to the resin (C). It is preferably 15 parts by mass or less, more preferably 0.001 to 10 parts by mass of 0.005 to 5 parts by mass. When the content of the acid diffusion controlling agent exceeds J, there is a problem of the sensitivity of the formed photoresist film or the development of the exposed portion. On the one hand, when it is less than 〇. 0 〇1 parts by mass, there will be a tributary shape or size loyalty of the photoresist film formed by the member, tributyloxy, hydrazine, hydrazide- ketamine, Ν-B. Ester, etc. methylurea, tri-n-butyl, piperazine, 卩戚fl-fixed morpholine, morpholinyl)-.2.2] octane species, may also be 100 parts by mass, preferably 5 parts by mass Declining system Article drop problem -53-201131299 [1--5] The sensitizing solvent (E) of the present invention, the radiation-resistant resin composition (I) containing a solvent (to be also referred to as "solvent (E)") are. The solvent (E) is exemplified by, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, propylene glycol monoalkyl ether acetate, lactic acid ester, formate, Acetates, propionates, esters, aromatic hydrocarbons, ketones, guanamines, lactones, and the like. These solvents may be used alone or in combination of two or more. The content of the solvent (E) is preferably such that the total solid content concentration of the sensitive radiation linear resin composition is from 1 to 70% by mass, more preferably from 1 to 15% by mass, and even more preferably from 1 to 10%. The amount of mass %. When the content is less than 1% by mass, the viscosity is too high, and it is difficult to apply. On the other hand, when it exceeds 70% by mass, it is difficult to form a photoresist film having a sufficient thickness. Further, the sensitive radiation linear resin composition of the present invention may have the above-mentioned acid generator (A), acid generator (B), resin (C), acid diffusion inhibitor (D), and other acid generators described later, and interfacial activity. The additive or the like is prepared by dissolving in a solvent (E) in such a manner that the total solid content concentration is within the above range. Further, after the preparation as described above, it is preferably filtered through a filter having a pore diameter of, for example, about 0.2 m. [1-6] Other sensitive radiation linear acid generator The photosensitive radiation linear resin composition (I) of the present invention may further be used in addition to the above-mentioned acid production-54-201131299 raw material (A1) and acid generator (B). Other sensitive radiation linear acid generators (hereinafter also referred to as "other acid generators") are formulated. Other acid generators include, for example, a gun salt compound, a sulfonic acid compound, and the like other than the acid generator (A 1 ) and the acid generator (B) described above. The iron salt compound is exemplified by, for example, an iodine salt, a phosphonium salt, a phosphonium salt, a diazo salt, and a pyridinium salt. Further, the sulfonic acid compound is exemplified by, for example, an alkylsulfonate, an alkylsulfonium iminoamine, a haloalkylsulfonate, an arylsulfonate, and an imidosulfonate. Among these other acid generators, specifically, for example, diphenyl iodide trifluoromethanesulfonate, diphenyl iodide pentafluoro n-butane sulfonate, diphenyl iodine perfluoro-n-octane Alkane sulfonate, bis(4-butylbutylphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodide nonafluoro-n-butane sulfonate, double (4 Tributyl phenyl) iodine gun perfluoro-n-octane sulfonate, cyclohexyl 2-oxocyclohexyl-methyl fluorene trifluoromethanesulfonate, dicyclohexyl • 2-oxocyclohexyl hydrazine Trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiindole Imine, nonafluoro-n-butanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo[2·2.1]hept· 5-ene-2,3-dicarbodiimide, hydrazine-hydroxysuccinimide trifluoromethanesulfonate, hydrazine-hydroxysuccinimide, nonafluoro-n-butane sulfonate, hydrazine-hydroxyamber Imine perfluoro-n-octane sulfonate, succinimide trifluoromethanesulfonate, triphenylsulfonium hexafluorobutane sulfonate Acid salt, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium-2-bicyclo[2.2.1]hept-2-yl-1,1-difluoroethanesulfonate, triphenylsulfonium- 2--55- 201131299 Bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-butoxy: naphthyltetrahydrothiophene hexafluorobutane sulfonate Acid salt and 4-butoxy-1-naphthylthiophene-2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethane sulfonate The acid generator may be used singly or in combination of more than one species. The content of the other acid generator is preferably from 0 to 80 parts by mass, based on 100 parts by mass of the green agent (A1), from the viewpoint of the sensitivity and the apparent property of the photoresist film formed of the linear radiation-sensitive resin group. More than 0 to 50 parts by mass, and the content of the other acid generator exceeds 80 parts by mass, and the resolution is lowered. [1-7] Other components The sensitive radiation linear resin composition (I) of the present invention comprises, in addition to the above-mentioned green agent (A1), acid generator (B), resin (C), acid diffusing agent (D), solvent (E) In addition to other acid generators, various additives such as surfactants, sensitizers, and aliphatic additives may be blended as other components. The above surfactant is a component which exhibits an effect of improving coatability, streaking, and development. Such surfactants may, for example, be polyoxyethylene lauryl ether oxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octyl ether, polyoxyethylene n-decyl phenyl ether, polyethylene A nonionic surfactant such as an alcohol dilaurate or a diol distearate, and the following 1 <^341 (manufactured by Shin-Etsu Chemical Co., Ltd.), ? 〇1^?1^0^^^〇· S -1- Tetrahydro hydrazine two-component acid production is good, acid production control - step addition, etc., polyphenyl polyethylate name 75, -56- 201131299 POLYFLOW No.95 (The above is manufactured by Kyoeisha Chemical Co., Ltd.), EF TOP EF301 ' EF TOP EF303, EF TOP EF352 (above is manufactured by TORKEMU PRODUCT), MEGAFAC F 1 7 1, MEGAFAC F173 (The above is Japanese ink Chemical Industry Company), FLORARD FC430, FLORARD FC431 (above Sumitomo 3M), ASAHIGUARD AG710, SURFLON S-3 82, SURFLON SC-1 01, SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-106 (above, manufactured by Asahi Glass Co., Ltd.). These surfactants may be used singly or in combination of two or more. The amount of the surfactant to be added is preferably 2 parts by mass or less, more preferably 1 to 2 parts by mass, per 100 parts by mass of the resin (C). The sensitizer is a linear resin composition having a radiation-sensing radiation, which exhibits energy for absorbing radiation, and transmits the energy to the acid generators (A1) and (B), thereby increasing the amount of acid generated. The effect of the appearance sensitivity. These sensitizers are exemplified by, for example, carbazoles, acetophenones, benzophenones, naphthalenes, phenols, hydrazinium, eosin (E 〇si η ), rosin, and dinaphthene ( Pyrenes), terpenoids, phenothiazines, etc. Further, these sensitizers may be used alone or in combination of two or more. The amount of the sensitizer to be added is preferably 20 parts by mass or less, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the resin (C). Further, the latent image of the exposed portion can be visualized by blending a dye or a pigment to mitigate the influence of the streaks at the time of exposure. Further, by including a further auxiliary agent, it is possible to change the adhesion between the film and the substrate of -57-201131299. The alicyclic additive is a component having an effect of further improving dry etching resistance, pattern shape, adhesion to a substrate, and the like. Examples of the alicyclic additive include 1-adamantanecarboxylic acid, 2-adamantanone, 1-butylantanecarboxylic acid tert-butyl ester, 1-adamantanecarboxylic acid tert-butoxycarbonylmethyl ester, and 1- Α-butyrolactone adamantane, di-t-butyl ester of 1,3·adamantane dicarboxylate, tert-butyl 1-adamantane acetate, tert-butoxycarbonyl methyl ester of 1-adamantane acetate, 1 , adamantane derivatives such as 3-adamantyl diacetate di-t-butyl ester, 2,5-dimethyl-2,5-di(adamantylcarbonyloxy)hexane; tert-butyl deoxycholate , third butoxymethyl methyl deoxycholate, 2-ethoxyethyl deoxycholate, 2-cyclohexyloxyethyl deoxyclay, 3-oxocyclohexyl deoxycholate, deoxycholate Deoxycholate esters such as tetrahydropyranyl ester, deoxycholic acid, and glyceryl triacetate; third butyl cholesterate; Oxyethyl ester, 2-cyclohexyloxyethyl lithate, 3-oxocyclohexyl lithate, tetrahydropyranyl lithate, valeric acid, and other lithocholic acid Ester; 3-[2-hydroxy-2,2-bis(trifluoromethyl)ethyl]tetracycline [6.2.1.13'6.0 2'7] dodecane and the like. Further, the alicyclic additives may be used singly or in combination of two or more. The content of the alicyclic additive is preferably 20 parts by mass or less, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the resin (C). When the content is more than 20 parts by mass, the heat resistance of the formed photoresist film may be lowered. Further, in addition to the additives, an alkali-soluble polymer may be formulated in an amount of -58-201131299 having an acid-dissociable protecting group. A low molecular alkali solubility control agent, an antihalation agent, a storage stabilizer, an antifoaming agent, and the like. [2] Sensitive radiation linear resin composition (II) The sensitive radiation linear resin composition of the present invention [hereinafter also referred to as "sensitive radiation linear resin composition (II)"] contains a specific sensitive radiation linear acid generator [hereinafter also It is called "acid generator (A2)"] and solvent. According to the sensitive radiation linear resin composition containing the acid generator (A2), the adverse effect on the environment or the human body is low, and a photoresist film which can obtain a good photoresist pattern can be formed. [2- 1 ] The radiation-sensitive linear acid generator (A2) The acid generator (A2) is represented by the following formula (1-2). Since the acid generator (A2) has a strong fluorine-containing electron-withdrawing group at the α-position of the sulfonyl group in its structure, a sulfonic acid having a high acidity is generated upon exposure or the like. Further, the acid generator (?2) has a high boiling point in addition to the function as a linear radiation acid generator, and is less volatile in the photolithography step, and shortens the diffusion distance of the acid in the photoresist film. That is, it has the proper characteristics of the diffusion length of the acid. [4 4 】* I MG [C44] 〇〇+Μ 0~S—(cF2·)~S—〇M+ (1_2) II \ / threshold [in general formula (I-2), Μ + represents a ruthenium cation represented by the following formula (2-1-1) and two Μ + may be the same or different from each other, and η represents 2 to 1 〇 -59 - 201131299

[In the formula (2-1-1), each A independently represents an oxygen atom or a single bond, and each B independently represents a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms; a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 25 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, wherein c, d and e each independently represent an integer of 0 to 2 'And at least one of c, d and e is 1 or 2]. The π in the formula (1-2) is an integer of 2 to 1 ,, preferably an integer of 2 to 6, more preferably 3 or 4. Further, the phosphonium cation represented by the formula (2-1-1) can be directly used as the description of the phosphonium cation represented by the formula (2 -1 -1 ) in the above-mentioned sensitive radiation linear resin composition (I). The respective methods for producing the sulfonic acid anion and the phosphonium cation in the acid generator (A2) can be directly used as described in the acid generator (A 1 ) in the above-mentioned radiation-sensitive linear resin composition (I). Further, the acid generator (A2) can be synthesized in the same manner as the acid generator (A1) in the above-mentioned sensitive radiation linear resin composition (I). Further, the sensitive radiation linear resin composition (Π) of the present invention may contain only one kind of the above acid generator (A2), or may contain two or more kinds. -60-201131299 The content of the acid generator (A2) in the sensitive radiation linear resin composition (II) of the present invention is usually 0.1 to 5 parts by mass based on 100 parts by mass of the resin (c) described later. It is 1 to 4 parts by mass, more preferably 5 to 3 parts by mass. When the content of the acid generator (A2) is less than 0.1 part by mass, it is difficult to sufficiently exhibit the desired effects of the present invention. On the other hand, when it exceeds 50 parts by mass, the transparency to the radiation, the shape of the pattern, and the heat resistance are lowered. [2-2] The sensitive radiation linear acid generator (B) The sensitive radiation linear resin composition (II) of the present invention preferably further comprises the above formula (X) in addition to the above acid generator (A2). Acid generator (B). In this case, the adverse effect on the environment or the human body is lower and a photoresist pattern capable of obtaining a good photoresist pattern can be formed. Further, as the acid generator (B), the description of the acid generator (B) of the above-mentioned radiation-sensitive linear resin composition (I) can be used as it is. Further, the sensitive radiation linear resin composition (II) of the present invention may contain only one acid generator (B), or may contain two or more kinds. The content of the acid generator (B) in the sensitive radiation linear resin composition (II) of the present invention is appropriately adjusted depending on the acid generator (A2) and, if necessary, the kind or content of other acid generators described later, but is relatively The resin (C) is preferably 30 parts by mass or less, more preferably 0.1 to 30 parts by mass, still more preferably 1 to 20 parts by mass, even more preferably 5 to 20 parts by mass, per 100 parts by mass. When the content of the acid generator (B) exceeds 30 parts by mass, the transparency, the shape of the pattern, and the heat resistance of the radiation may be lowered. -61 - 201131299 [2-3] Resin (C) The sensitive radiation linear resin composition (II) of the present invention contains an alkali-insoluble or alkali-insoluble resin containing a repeating unit having an acid-dissociable group (hereinafter also referred to as "resin (C)"). Further, the resin (C) may be directly used as the resin (C) in the above-mentioned sensitive radiation linear resin composition (I). Further, the sensitive radiation linear resin composition (II) of the present invention may contain only one resin ( C) may also contain two or more types. [2-4] Acid Diffusion Control Agent (D) The sensitive radiation linear resin composition (II) of the present invention is preferably other than the above-mentioned acid generator (A2), acid generator (B), and resin (C). An acid diffusion controlling agent (hereinafter also referred to as "acid diffusion controlling agent (D)") is contained. Further, the acid diffusion controlling agent (D) can be directly used as described for the acid diffusion controlling agent (D) in the above-mentioned sensitive radiation resin composition (I). Further, the sensitive radiation linear resin composition (II) of the present invention may contain only one acid diffusion controlling agent (D), or may contain two or more kinds. [2-5] Solvent (E) The radiation sensitive linear resin composition (Π) of the present invention is a solvent (hereinafter also referred to as "solvent (E)"). Further, the solvent (E) can be directly used as the solvent (E) in the above-mentioned sensitive radiation linear resin composition (I). Further, the sensitive radiation linear resin composition (II) of the present invention may contain only one solvent (E), and may contain two or more kinds. [2-6] Other sensitive radiation linear acid generator The sensitive radiation linear resin composition (Π) of the present invention can be further formulated with other sensitive radiation in addition to the above acid generator (A2) and acid generator (B) Linear acid generator (hereinafter also referred to as "other acid generator"). Further, as the other acid generator, the description of the other acid generator in the above-mentioned sensitive radiation linear resin composition (I) can be directly used. Further, the radiation sensitive linear resin composition (11) of the present invention may contain only one other acid generator, and may contain two or more kinds. [2-7] Other components The sensitive radiation linear resin composition (11) of the present invention, in addition to the above acid generator (A 2 ), acid generator (B) 'resin (C), acid diffusion controlling agent (D) In addition to the solvent (E) and other acid generators, various additives such as a surfactant, a sensitizer, and an aliphatic additive as other components may be further blended. Further, in addition to the additives, an alkali-soluble polymer, 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 may be formulated. Further, each of the above components can be directly used as described in the above-mentioned sensitive radiation linear resin composition (I). Further, each of the components may be used alone or in combination of two or more. -63- 201131299 [3] Novel compound The novel compound of the present invention is characterized by the following formula (1-2). [化 4 6 ]* I MG [C46]

[In the formula (1-2), M + represents an anthracene cation represented by the following formula (2-1-1), and two M + may be the same or different from each other, and η represents an integer of 2 to 10],

[In the formula (2-1-1), each oxime independently represents an oxygen atom or a single bond, and each B independently represents a substituted or unsubstituted linear or branched alkyl group having 1 to 12 carbon atoms; a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 25 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, wherein c, d and e each independently represent an integer of 0 to 2 And at least one of c, d, and e is 1 or 2]. η in the formula (1-2) is an integer of 2 to 10, preferably an integer of 2 to 6, more preferably 3 or 4. -64- 201131299 The description of the mirror cation represented by the general formula (2 -1 -1 ) in the above-mentioned sensitive radiation linear resin composition (I ) can be directly used as the phosphonium cation represented by the formula (2-1-1). . The novel compound of the present invention can be used as a sensitive radiation linear acid generator in a sensitive radiation linear resin composition. In particular, an acid generator (A 1 ) or (A 2 ) as the above-mentioned sensitive radiation linear resin composition can be used. Among the above novel compounds, the respective methods for producing the sulfonic acid anion and the phosphonium cation can be directly used as described in the acid generator (A 1 ) in the above-mentioned sensitive radiation linear resin composition (I). Further, the novel compound can be synthesized in the same manner as the acid generator (A1) in the above-mentioned sensitive radiation linear resin composition (I). [4] Formation of resist pattern The sensitive radiation linear resin composition of the present invention can be used as a material which can be formed into a chemically amplified positive type resist film. In the chemically amplified positive type resist film, the acid dissociative group in the resin (C) is removed by the action of an acid generated by exposure of the acid generator (A1) or (A2), so that the resin (C) becomes Alkali soluble. That is, an alkali-soluble portion is produced in the photoresist film. The alkali-soluble portion is an exposed portion of the photoresist, and the exposed portion can be dissolved and removed by the alkali developing solution. Thus, a positive resist pattern of a desired shape can be formed. The details are explained below. The photoresist pattern is formed using the sensitive radiation linear resin composition of the present invention. First, a photoresist film is formed from the sensitive radiation linear resin composition of the present invention. As for the sensitive radiation linear resin composition, for example, a filter having a pore diameter of about 0.2/zm can be used after adjusting the total solid content concentration as described above -65-201131299. The sensitive radiation linear resin composition is applied onto a substrate such as a tantalum wafer or an aluminum-coated wafer by a suitable coating means such as spin coating, cast coating, or roll coating to form light. Block the film. Then, depending on the case, heat treatment (hereinafter referred to as "PB") may be carried out at a temperature of about 70 to 160 °C in advance. Next, the photoresist film is exposed in such a manner as to form a predetermined photoresist pattern. The radiation used for the exposure may be, for example, a KrF excimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength: 193 nm), EUV (extreme ultraviolet light, a wavelength of 13.5 nm, etc.), etc. X-rays such as synchrotron radiation, charged particle beams such as electron beams, and the like. Further, the exposure conditions such as the amount of exposure can be appropriately selected depending on the formulation of the linear composition of the radiation sensitive resin or the type of the additive. Further, the exposure may be a liquid immersion exposure. After exposure, it is preferably subjected to heat treatment (hereinafter referred to as "PEB"). By the PEB, the detachment of the acid dissociable group of the resin (C) can be smoothly carried out. The heating condition of the PEB may be appropriately selected depending on the compounding composition of the sensitive radiation linear resin composition, but is preferably from 30 to 200 ° C, more preferably from 50 to 170 ° C. In the present invention, in order to maximize the extraction of the sensitive radiation linear resin The organic or inorganic anti-reflection film is formed on the substrate to be used, as disclosed in, for example, Japanese Patent Publication No. Hei. No. Hei. No. Hei. By. Further, in order to prevent the influence of the alkaline-based impurities contained in the environmental atmosphere, it is provided on the photoresist film as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. These technologies. Next, the exposed photoresist is imaged by the film. The developing solution used in the development is preferably, for example, potassium oxydissolvate, sodium carbonate, sodium citrate, sodium metasilicate, propylamine, diethylamine, di-n-propylamine, triethylamine, ethyldi Basic compounds such as methylamine, triethanolamine, piperidine hydroxide, choline '1,8-diazabicyclo[5.4.0]-7·azabicyclo[4.3.0]-5-decene; aqueous solution . The concentration of the alkaline aqueous solution is preferably 1 〇. If the concentration of the solution exceeds 10% by mass, there is a case of non-exposure. Further, the developing solution is preferably a pH 8 to I4, and a developing solution solvent composed of an alkaline aqueous solution. The organic solvent can be exemplified by a ketone such as acetone, methyl butyl ketone, cyclopentanone, cyclohexanone or 3-methylcyclopentanone; methanol, ethanol, n-propanol, iso-tributanol, cyclopentanol Alcohols such as cyclohexanol and 1,4-hexanediol; ethers such as tetrahydrofuran and dioxane; esters such as ethyl ester and isoamyl acetate; toluene, xylenol, etidylacetone and dimethylformate Amidoxime and the like. One type may be used, or two or more types may be used in combination. The blending amount of the organic solvent is preferably 100 parts by volume or less based on the alkaline water. If the organic solvent is a protective film. Alternatively, it may be formed by the formation of a predetermined photoresist pattern of sodium hydroxide, hydrogen water, ethylamine, n-ylamine, methyldiethyltetramethylammonium, pyrrole, undecene, and 5-diene. One type is less than or equal to alkaline. If the alkaline water portion is also dissolved in the image, it is preferably pH 9 to 14. For example, an aromatic ethyl ketone, methyl isoindole, 2,6-dimethylcyclopropanol, n-butanol, a first, 1,4-hexane dimethanolate, or an n-butyl acetate may be added. Hydrocarbons, or other organic solvents can be used in a single solution of 100 parts by volume. When the amount exceeds I 00 body-67-201131299, the development is reduced, and the exposure of the exposed part is large, and the composition is composed of an alkaline aqueous solution. It can also be added in an appropriate amount in the liquid. Further, it was developed with a developing solution composed of an alkaline aqueous solution, and dried. [Examples] The following examples are given to more specifically illustrate the practice of the present invention, and the present invention is not limited by the examples. Among them, "%" is a quality standard unless otherwise specified. Synthesis of π] Resin and Acid Generator (Synthesis Example 1-1) Synthesis of Resin (C-1) 53 g of p-ethoxylated styrene and the following formula (M-1) (hereinafter referred to as "compound" (Ml)") 48 g, 7 g of an acrylonitrile (hereinafter referred to as "AIBN"), and a tris-dodecyl thiosulfate in 150 g of propylene glycol monomethyl ether, and then maintained at 70 ° C under a nitrogen atmosphere. Polymerization for 16 hours. After the polymerization, the droplets were added to 1000 g of n-hexane to coagulate and purify the copolymer. Then, 150 g of propylene glycol monomethyl ether was added to the copolymer, and 150 g of methanol, 37 g of triethylamine and 7 g of water were added, and the boiling point was The hydrolysis reaction was carried out for 8 hours. After the reaction, the amine was distilled off under reduced pressure, and the obtained copolymer was dissolved in 150 g of acetone and then solidified in 2 000 g of water, and the resulting white powder was filtered and dried overnight at 50 ° C. The active agent is washed in water. However, the "parts" and the indicated nitrogen diisobutanol U dissolve to dissolve the reaction. Then, after that, the following reflux agent and triethyl hydrate were added under reduced pressure -68-201131299. The copolymer obtained had a Mw of 6000 and a Mw/Mn of 1.9. The 13C analysis result was derived from p-hydroxystyrene. The content ratio (m〇1 ratio) of the repeating unit to the repeating unit derived from the grazing J (Μ-1) is 6 〇: The copolymer is hereinafter referred to as the resin (C-1). -NMR ί化40的 [化 4 8 】* I MG [C48]

(Synthesis Example 1-2) Synthesis of Resin (C-2) 55 g of p-ethoxylated styrene, represented by formula (M-2); (hereinafter referred to as "compound (M-2)") 45 g, AIBN 4 g Tri-dodecyl mercaptan lg was dissolved in propylene glycol monomethyl ether 10 c 0 gc| 'The reaction temperature was maintained at 70 ° C under a nitrogen atmosphere, and polymerization was carried out. After the polymerization, the reaction solution was added dropwise to 100 g of n-hexane, and the polymer was solidified and purified. Next, 150 g of propylene glycol monomethyl ether was again added to the copolymer, followed by the addition of 150 g of methanol and 34 g of tri-Z 6 g of water, and the reaction was carried out by refluxing at the boiling point, followed by hydrolysis reaction 8 / J reaction, followed by distillation under reduced pressure. After removing the solvent and triethylamine, the obtained copolymer container was placed in 1,500 g of acetone, and then added dropwise to 200 g of water to solidify, and the blue-white powder was filtered, and dried under reduced pressure at 50 ° C overnight. The obtained copolymer had Mw of 10,000 and Mw/Mn of 2.1. Compounding and after the first 1 6 small addition of t-amine and ‘time. 13C--69- 201131299 NMR Analysis Township & ι πτ/ΓΜ聚' is the content ratio of the repeating unit derived from p-hydroxystyrene and the repeating unit derived from the compound (Μ·2) ( The copolymer of m〇1 ratio) is 6 Π t copolymer, which is called resin (C2). [化4 9 ]* I MG [C49] (M-2)

(Synthesis Example 1-3) Synthesis of Resin (c-3) A compound represented by the following formula (M-3) (hereinafter also referred to as "compound (M-3)") 31 63 g (35 mol%), and the following formula ( Compound represented by m-4) (hereinafter also referred to as "compound (M-4)") 49.6 〇g (45 mol%) 'Compound represented by the following formula (M-5) (hereinafter also referred to as "compound (M) -5)" 6.45 g (10 mol%) was dissolved in 200 g of 2-butanone' followed by 2,2'-but bis(2-methylpropionitrile) 8.Hg to prepare a monomer solution. The above compound (M-2) 12.32 g (1 〇〇〇〇 mol, 2 - butanone i〇〇g of 1 〇〇〇〇 11 three-necked flask for one minute) was purged with nitrogen, and the mixture was heated while stirring. To the above, using a dropping funnel, the previously prepared monomer solution was added dropwise over 3 minutes. The polymerization was started for 6 hours starting from the start of the dropwise addition. After the completion of the polymerization, the polymerization was carried out by water cooling. The solution was cooled to 30 ° C or lower, and 4000 g of methanol was charged, and the precipitated white powder was filtered. The filtered white powder -70-201131299 was dispersed in 400 g of methanol to be slurried. After the filtration, the filtration operation was carried out twice, followed by vacuum drying at 50 ° C for 17 hours to obtain a white powder (copolymer). The obtained copolymer had a Mw of 4,300 and a Mw / Mn of 1.30, as a result of l3C-NMR analysis, The content of each repeating unit represented by (M-2), compound (Μ3), compound (Μ·4), and compound (Μ-5) is 8.9: 35.6: 46.2: 9.3 (mol%) copolymer [化5 Ο]* I MG [C50]

(Μ-3) (Μ-4) (Μ-5) (Synthesis Example 2-1) Synthesis of an acid generator (Α-1) The compound represented by the following formula (X-1) is 8. 8 g, the following formula (X-2) represented by the compound 3.9 g, water l〇〇g, dichloromethane i〇0 g, and stirred at room temperature for 3 hours. After the completion of the stirring, the organic layer was recovered, and the organic layer was washed 8 times with 5 g water. Subsequently, the organic layer of dichloromethane was distilled off under reduced pressure, and the obtained solid was dried at 50 ° C for 12 hours. The obtained copolymer was analyzed by NMR analysis of I η - N M R and 19 F- -71 - 201131299, and was a compound represented by the following formula (A-1) [Chem. 5 1 J * I MG [C51]

[化 5 2 ]* I MG [C52] s ten cr (x-1) Ο F F F Ο

j. — IIK o~s- II -S-〇- κ+ (X-2) O F F F Ο 【化 5 3 I * I MG [C53]

(A-1) (Synthesis Example 2-2) Synthesis of the acid generator (A-2): 6.0 g of the compound represented by the following formula (χ·3), 39 g of the compound represented by the above formula (X-2), and water were mixed. I〇〇g, dichloromethane i〇〇g, and stirred at room temperature for 3 hours. After the completion of the stirring, the organic layer was recovered, and the organic layer was washed 8 times with 5 g of water. Subsequently, the organic layer of dichloromethane was distilled off under reduced pressure, and the obtained solid was dried at 5 ° C for 12 hours. The obtained copolymer was analyzed by ih_NMr and i9F_NMR to give a compound represented by the following formula (a_2). •72- 201131299 【化5 4 】* I MG [C54]

〈》-S + ΟΓ (X-3) b

[化 5 5 ]* I MG [C55]

(A-2) (Synthesis Example 2-3) Synthesis of the acid generator (A_3): 7.5 g of the compound represented by the following formula (X-4) and 3.9 g of the compound represented by the above formula (X-2), water i 〇〇g, dichloromethane i〇〇g, and stirred at room temperature for 3 hours. After the completion of the stirring, the organic layer was recovered, and the organic layer was washed 8 times with 50 g of water. Subsequently, the organic layer of dichloromethane was distilled off under reduced pressure, and the obtained solid was dried at 50 ° C for 12 hours. The result of the analysis of the obtained copolymer by iH_Nmr and NMR was a compound represented by the following formula (A-3). [化 5 6 ]* I MG [C56]

-73- 201131299 【化5 7 】* I MG [C57]

(A-3) Further, in the measurement of the weight average molecular weight (Mw) and the number average molecular weight (?n) in the present embodiment, a GPC column (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by TOSOH Co., Ltd. was used. The flow rate: 1.0 ml/min; elution solvent: tetrahydrofuran; column temperature: 40 ° C, using monodisperse polystyrene as a standard, and determined by gel permeation chromatography (GPC). Further, the degree of dispersion Mw/Mn was calculated from the measurement results. Further, 'iH-NMR, l3C-NMR, and &quot;F-NMR analysis were measured using a model "JNM-ECX400" manufactured by Nippon Denshi Co., Ltd. [2] Preparation of sensitive radiation linear resin composition (Example 1) As shown in Table 1, 100 parts of the resin (C-1) prepared in the synthesis example (1-1) and an acid generator (A-1) were mixed. 20 parts, 2 parts of acid generator (B-1), 1 part of acid diffusion controlling agent (Dl), 2500 parts of solvent (E-1), and solvent (E-2) 1 100 parts of film having a pore diameter of 200 nm The resulting mixture was filtered by a filter to thereby modulate the composition of the radiation-sensitive linear resin composition-74-201131299 (Examples 2 to 13 and Comparative Examples 1 to 3) with the feed amount shown in Table 1, mixed resin ( C), an acid generator (A), an acid generator (B), an acid diffusion controlling agent (D), and a solvent (E), and the resulting mixed liquid was filtered through a membrane filter having a pore diameter of 200 nm, thereby modulating Examples 2 to 1 3 and each of the composition solutions of Comparative Examples 1 to 3 (sensitive radiation linear resin composition). -75- 201131299 [Table i] Resin (C) Acid Repellent 丨gsheng [A) Acid Production" (B Μ ) Acid Diffusion Control Agent CD) Solvent (E) Type Content Type Content Type Content Type Content Content (Part) (Part) (Part) (Part) Ώ Example 1 C-1 100 Α-1 20 B-1 2 D-1 2 E-1/E-2 2500/1100 贲Example 2 C-1 100 Α-1 20 B-1 2 E-1/E-2 2500/1100 贲Example 3 C-2 100 Α-1 20 B-2 2 . E-1/E-2 2500/1100 Case 4 C -1 100 Α-2 20 B-1 2 D-1 1 E-1 3600 贲Example 5 C-1 100 Α-1 20 D-1 1 E-1/E-2 2500/1100 Case 6 C- 1 100 Α-1 20 B-1 2 D-1 1 E-1/E-2 2500/1100 Ϊ! Example 7 C-1 100 Α-1 20 B-1 2 _ E-1/E-2 2500 /1100 Example 8 C-1 100 Α-3 20 B-1 2 D-1 1 E-1/E-2 2500/1100 Case 9 C-1 100 Α-3 20 B-1 2 E-1 /E-2 2500/1100 Example 10 C-1 100 Α-3 20 B-1 2 D-1 1 E-1/E-2 2500/1100 Example 11 C-1 100 Α-3 20 B- 1 2 - E-1/E-2 2500/1100 Example 12 C-3 100 Α-3 13 B-1 13 D-1 2 E-1/E-3 1100/2500 W Example 13 C-3 100 Α-3 13 _ D-1 6 E-1/E-3 1100/2500 Comparative Example 1 C-1 100 a-1 20 B-1 2- E-1/E-2 2500/1100 Comparative Example 2 C -1 1 00 a-1 20 B-1 2 _ E-1/E-2 2500/1100 Comparative Example 3 C-3 100 a-1 13 - D-1 2 E-1/E-3 1100/2500 Further, Table 1 The details of the acid generator (A), the acid generator (B), the resin (C), the acid diffusion controlling agent (D), and the solvent (E) are as follows. <Acid generator (A) &gt; (A-1): The acid generator (A-1) (A-2) obtained in the above Synthesis Example (2-1): obtained in the above Synthesis Example (2-2) Acid generator (A--76-2) 201131299 (A-3): Acid generator (A-(a-1) obtained in the above Synthesis Example (2-3): by the following formula (a-1) Compound represented by [5-8]* I MG [C58]

(a-1) <Acid generator (B)> (B-1): a compound represented by the following formula (B-1): a compound represented by the following formula (B-2)

(B-1)

(B-2) -77-201131299 <Resin (c)> (cl): Resin (Cl) (C-2) obtained in the above Synthesis Example (1-1): obtained in the above Synthesis Example (1-2) Resin (C-2) (C-3): Resin (C-3) obtained in the above Synthesis Example (1-3) <Acid Diffusion Control Agent (D)> (D-1): Tri-n-octyl Amine <solvent (E ) > (E-1 ): ethyl lactate (E-2): propylene glycol monomethyl ether acetate (E-3): cyclohexanone [3 -1 ] sensitive radiation linear resin composition Evaluation (EB exposure) The composition solution (the respective photosensitive radiation linear resin compositions of Examples 1 to 5, 8, and 9 and Comparative Example 1) was spin-coated in CLEAN TRACK ACT-8 manufactured by Tokyo Electronics Co., Ltd. After the wafer was mounted on the wafer, PB (heat treatment) was carried out under the conditions shown in Table 2 to form a photoresist film having a film thickness of 50 nm. Subsequently, the resist film was irradiated with an electron beam using a simple electron beam drawing device (manufactured by Hitachi, Ltd., type "HL8 00D", output: 50 KeV, current density: 5.0 A/cm2). After the electron beam was irradiated, PEB was carried out under the conditions shown in Table 2. Subsequently, using a 2.38% aqueous solution of tetramethylammonium hydroxide, it was developed by a paddle stirring method at 23 ° C for 1 minute, and then washed with pure water and dried to form a photoresist pattern. -78- 201131299 Various evaluations were made on the thus formed photoresist pattern, and the evaluation results are shown in Table 2. (3-1-1) Sensitivity (L/S) such that a line portion '1' from a line width of 1 〇 nm and a space formed by an adjacent line portion are 1 10 nm (ie, a groove) The pattern (the so-called line and space pattern (1 L 1 S)) forms an exposure amount of 1 line width as an optimum exposure amount, and the sensitivity (pC/cm 2 ) is evaluated by the optimum exposure amount. (3-1-2) Nano-edge roughness (i) Using a scanning electron microscope for semiconductors (high-decomposition energy FEB length measuring device, trade name "S-9220", manufactured by Hitachi High-Tech Co., Ltd.) to observe the design line width I 1 Onm Line pattern of line and interval (1 L 1 S ). With respect to the observed shape, as shown in FIGS. 1 and 2, the photoresist film formed on the germanium wafer 1 was measured by using a CD-SEM ("S-9220" manufactured by Hi-Tech Co., Ltd.). The difference between the line width at which the unevenness of the lateral side 2a of the line portion 2 is formed and the design line width of 1 l 〇 nm "△ (: 〇", evaluation of the nano edge roughness. Further, in Figs. 1 and 2 The unevenness is more exaggerated than the actual. (3-1-3) Resolution (L/S) For line and interval (1 L 1 S ), the minimum width (nm) of the line pattern with the optimum exposure is used as the resolution. [3-2] Evaluation of sensitive radiation linear resin composition (KrF exposure) -79- 201131299 In the CLEAN TRACK ACT-8 manufactured by Tokyo Electronics Co., Ltd., the composition solution (Examples 6 to 7, 10, 1) 1 and the respective sensitive radiation linear resin compositions of Comparative Example 2) were spin-coated on a tantalum wafer, and PB (heat treatment) was carried out under the conditions shown in Table 3 to form a photoresist film having a film thickness of 50 nm. Using the product name "Scanner NSR-S203B" (manufactured by Nikon, opening number = 0.68, σ = 0.75), it was exposed through a double mask, and it was shown in Table 3. The conditions were carried out. Subsequently, a 2.38% aqueous solution of tetramethylammonium hydroxide was used, and the image was developed at 23 ° C for 30 seconds by a paddle stirring method using an LD nozzle, washed with pure water, and dried to form light. The resistance pattern type 进行 performs various evaluation tests on the photoresist pattern thus formed, and the evaluation results thereof are shown in Table 3. (3-2-1) Sensitivity (L/S) so that the line width is 1 1 〇 nm A pattern formed by a partition (i.e., a groove) formed by an interval of 1 1 Onm formed by adjacent line portions (so-called line and space pattern (1 L 1 S )) forms a 1-to-1 line width The exposure amount is used as the optimum exposure amount, and the sensitivity (mJ/cm2) is evaluated by the optimum exposure amount. (3-2-2) Nano edge roughness (i) Scanning electron microscope using a semiconductor (high-decomposition energy FEB length measuring device) , the product name "S-922〇", manufactured by Hitachi High-Technologies Co., Ltd.) Observe the line pattern of the design line width of 1 1 〇nm line and interval (1 L 1 S ). For the shape observed, as shown in Figure 1 and As shown in Fig. 2, by using a CD-SEM ("S-9 2 20" manufactured by Hitachi-80-201131299 Hi-Tech Co., Ltd.), the photoresist film formed on the crucible is measured. The difference between the line width at which the unevenness of the lateral side 2a of the line portion 2 is formed and the design line width of 1 l 〇 nm is "ACD", and the edge roughness is evaluated. Further, the unevenness shown in Figs. 1 and 2 is more realistic than that [ 3-3] Evaluation of Sensitive Radiation Linear Resin Composition (ArF Exposure) Using a sensitive radiation linear resin composition on a 12 Å wafer forming a lower antireflection film ("ARC66", manufactured by Nissan Chemical Co., Ltd.) Each of the various radiation-sensitive linear resins of Comparative Example 3 was composed into a film having a film thickness of 75 nm, and PB was carried out under the conditions shown in Table 4. The composition for forming an overlayer film described in WO 2008/047678 was spin-coated on the formed film, and a coating film having a film thickness of 90 nm was formed by PB (90 ° C). The film was exposed by a transmission type using an ArF excimer laser exposure apparatus ("NSR-S61 0C", manufactured by Nikon Corporation, NA = 1.30, ratio = 0.800, Annular). After exposure, take the strip PEB shown in Table 3. Subsequently, a 2.38% aqueous tetramethylammonium hydroxide solution was used for liquid development, and dried to form a positive photoresist pattern. Various evaluation tests were carried out on the thus formed photoresist pattern, and the results are shown in Table 4. (3-3_1) MEEF (Photomask Error Enhancement Factor) Exposing the target size to 50nmlL/lS pattern exposure under the above evaluation conditions to form a line width of 50nm and a spacer (LS) pattern wafer 1 significant nano edge sheet . The company system (implementation) shape is followed by &gt; Example 1 for 60 seconds of immersion immersion), and the reticle image is used for imaging evaluation of the exposure of the aperture type -81 - 201131299 The amount of light is used as the optimum exposure amount. Then, using the optimum exposure amount, the target size of the line width is used as a mask pattern of 46 nm, 48 nm, 50 nm, 52 nm, and 54 nm, and the LS pattern of the pitch l〇〇nm is formed, and the length of the Hitachi system is SEM: CG4 0 00 The line width formed on the photoresist film was measured. At this time, the slope of the straight line when the target size (nm) is plotted on the horizontal axis and the line width formed on the photoresist film on each of the mask patterns is plotted on the vertical axis is calculated as Μ E E F . Moreover, the lower the MEEF, the lower the cost of mask production. (3-3-2) Nano edge roughness (ii) Exposure to the mask pattern of the target size of 50nmlL/1.8S by the above evaluation conditions, thereby forming an exposure pattern of a line width of 5 Onm S is the optimum exposure. For the observation of the 50nmlL/1.8 S pattern obtained with the optimum exposure amount, the SEM of the Hitachi system SEM: CG4000 is observed from the top of the pattern, and the line width of 10 points is observed at any point, and the measurement is performed by 3σ. The deviation is the nanoedge roughness (LWR). In addition, the smaller the LWR, the better the linearity of the pattern. (3-3-3) Minimum collapse size The reticle with a target size of 50 nmL/1.8S was passed through the above evaluation conditions, and the exposure was performed while changing the exposure amount of lm]/cm2. The line width of the pattern formed by the exposure amount of the lmJ/crn2 which is smaller than the exposure amount of the line collapse was measured by the length measuring SEM (manufactured by Hitachi, Ltd., model "CG4000") as the minimum collapse size. • 82- 201131299 Again, the smaller the squat, the higher the resistance to pattern collapse. Table 2] PB Condition PEB Condition Exposure Light Sensitivity (μΟ/ατι2) Nano Edge Roughness (nm) Resolution (nm) Temperature (°C) Time (seconds) Temperature (°c) Time (seconds) Example 1 130 60 130 60 EB 49 11 60 Example 2 130 60 130 60 EB 45 12 60 Example 3 130 60 110 60 EB 46 12 70 Example 4 130 60 130 60 EB 46 14 70 Example 5 130 60 130 60 EB 39 15 80 Example 8 130 60 130 60 EB 48 10 60 Example 9 130 60 130 60 EB 43 10 60 Comparative Example 1 130 60 130 60 EB 42 19 100 Table 3] PBi 1 Conditional PEB Condition Exposure Light Sensitivity (μΟ/〇 Γη2) Nanoedge Roughness (nm) Temperature ro Time (seconds) Temperature ΓΟ Time (seconds) Example 6 130 60 130 60 KrF 38 11 Example 7 130 60 130 60 KrF 35 13 Example 10 130 60 130 60 KrF 35 10 Example 11 130 60 130 60 KrF 31 11 Comparative Example 2 130 60 130 60 KrF 45 17 -83- 201131299 [Table 4] ΡΒ| m PEB Conditioned Exposure Light MEEF Nano Edge Roughness (nm) Minimum Collapse Size (nm) Temperature CC) Time (seconds) Temperature ΓΟ Time (seconds) β Example 12 120 60 100 60 ArF 2.5 4.5 32 Example 13 120 60 100 60 ArF 3.0 5.0 38 Comparative Example 3 120 60 100 60 ArF 4.0 5.5 40 From Table 2, Table 3 and Table 4, it can be understood that the following examples 1 to 13 contain a specific acid generator. The radiation-sensitive linear resin composition can effectively induce an electron beam or an ultraviolet ray, which is low in roughness, and can be formed into a film with high precision and stability, compared with the sensitive radiation linear resin composition of Comparative Examples 1 to 3. A fine-grained chemically amplified positive-type photoresist film. [Industrial Applicability] The sensitive radiation linear resin composition of the present invention is excellent not only in line and interval pattern but also in excellent edge roughness when forming a photoresist pattern, so it can be used for EB, EUV. Or a fine pattern of X-rays is formed. According to the invention, the sensitive radiation linear resin composition of the present invention is extremely useful as a chemically amplified photoresist which can be used for the production of semiconductor devices which are expected to be further miniaturized in the future. The novel compound of the invention can be used as a sensitive radiation linear acid generator in a sensitive radiation linear resin composition. [Simple description of the drawing] Fig. 1 is a plan view of a mode when the line pattern is viewed from above. -84- 201131299 Figure 2 is a schematic cross-sectional view of the line shape. [Main component symbol description] 1 : Substrate 2 : Photoresist pattern 2a : Transverse side of photoresist pattern -85-

Claims (1)

201131299 VII. Patent application scope: [In the formula (1-1), M + represents a phosphonium cation represented by the following formula (2), and two M+s may be the same or different from each other, and η represents an integer of 2 to 10] &gt; [Chemical 2] * I MG [C02] R, R2 &lt; 3 R (2 [In the general formula (2), R1, ^· and R are independently unsubstituted or unsubstituted, and the carbon number is 1 to 1 直. Or a branched ortho' or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms or two or more of R1, R2 and R3 bonded to each other to form a ring together with a sulfur atom in the formula] 3 】 * I MG [C03] R5 L 丫-(X) R6 R7 [In the general formula (X), R5, r6 and r7 independently represent a substituted or unsubstituted carbon number ι~ι〇 linear chain Shaped or branched (or substituted or not -86- 201131299 substituted aryl group 6 to 18' or any two or more of r5, r6 and r7 are bonded to the sulfur atom in the formula Forming a ring 'Y is a residual acid anion> 2. A type-sensitive radiation linear resin composition' characterized by containing a sensitive radiation linear acid generator represented by the following formula (I-2) and a solvent 'Chemical 4 】* I MG [C04] 〇0 +M ~ -S-fcF2-}-S-〇&quot; M+ (1,2) 〇Ο [In the formula (I-2), Μ + represents a phosphonium cation represented by the following formula (2-1-1), two Μ + can be the same or different from each other, n represents an integer from 2 to 10], [Chemical 5 I MG [C05] 八 八 n (2-1-1) e tAfO&quot; b)c ^ 1 (2-1-1) 'each A independently of each other represents an oxygen atom or a single bond, each of which is unsubstituted or unsubstituted a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alicyclic diyl group having 5 to 25 carbon atoms, or a substituted or unsubstituted carbon number The aryl group of 6 to 12, c, "and e" are independently of each other, "an integer of 2, and at least one of c, ... is 1 or 2]. The chemical substance is characterized by the following general formula (1 - 2) ) -87- 201131299 I * 6 + M + Μ -ο- onsno )^ 2 -—- F C06 and ^ OMSno Μ I .〇2) I II, I 翘] [S 阳数式同通说The following table can also be used to indicate the phase of the M+Pecon» + 中 中 } 2-2 2 2 η 镝 镝 ο ο ο I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I c 〇e [In the formula (2-1-1), each A independently represents an oxygen atom or a single bond, and each B independently represents a substituted or unsubstituted carbon number of 1 to 12 linear or branched. An alkyl group, a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 25 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and c, d and e independently of each other represent 0 to An integer of 2, and at least one of c, d, and e is 1 or 2]. 4. A compound according to claim 3, which is a radiation sensitive linear acid generator. -88-