TW200923579A - Radiation-sensitive composition - Google Patents

Abstract

Disclosed is a radiation-sensitive composition containing a polymer (A) having a repeating unit (1) represented by the general formula (1-1) below, a repeating unit (2) represented by the general formula (1-2) below and a repeating unit (3) having an acid-cleavable group, and a radiation-sensitive acid generator (B).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor substrate manufacturing step such as 1C, a circuit substrate such as a liquid crystal or a thermal head, and a sensitive radiation linear composition used in other photolithography steps. More specifically, it relates to an exposure light source such as a far-ultraviolet light having a wavelength of 220 nm or less, for example, an ArF excimer laser or an electron beam or the like as a light source, which is preferably a sensitive radiation linear composition in the photolithography step. [Prior Art] The chemically amplified type sensitive radiation linear composition is irradiated to the exposed portion to generate an acid by radiation such as a far-ultraviolet light represented by a KrF excimer laser or an ArF excimer laser, and the acid is used as a catalyst. The reaction changes the dissolution rate of the developing solution for the exposed portion and the unexposed portion to form a photoresist pattern composition on the substrate. When a KrF excimer laser is used as a light source, a chemically amplified radiation sensitive linear resin containing a poly(hydroxyphenethyl) (PHS) as a basic skeleton as a main component is used by using a 24 8 nm region. The composition can achieve high sensitivity while achieving high resolution and is a good pattern. On the one hand, in order to achieve further microfabrication of the photoresist pattern, for example, using a shorter wavelength source such as an ArF excimer laser (193 nm), a compound having an aromatic group such as PHS is substantially displayed in the region of 93 nm. Great absorption, so there are problems that are difficult to apply. Therefore, a radiation sensitive linear resin composition containing a resin having an alicyclic hydrocarbon skeleton which does not have a large absorption in the 193 nm region can be used as a lithographic material using an ArF excimer laser. -4-200923579 Further, it has been found that when a resin having the above alicyclic hydrocarbon skeleton contains a repeating unit having a certain lactone skeleton, the performance as a photoresist can be improved. For example, Patent Documents 1 and 2 describe a radiation sensitive linear resin composition using a resin containing a repeating unit having a mevalonolone skeleton or a γ-butyrolactone skeleton. Further, Patent Documents 3 to 13 describe a radiation sensitive linear resin composition using a resin containing a repeating unit having an alicyclic lactone skeleton. However, as shown in the above-mentioned patent documents and the like, when the resolution performance is simply improved, it is difficult to mix various requirements such as 9 Onm or less. In the future, due to the advancement of miniaturization, not only the resolution of the image is improved, but also the material development that is applicable in the immersion exposure step that is currently being applied is also required. Specifically, it is required to provide materials that can meet various characteristics such as Line Width Roughness (LWR), defect performance, PEB temperature dependence, and pattern dumping. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 9- 7 3 1 7 3 [Patent Document 2] U.S. Patent No. 6 3 8 8 1 0 1 [Patent Document 3] Japanese Special Opening 2 0 0 0 - 1 5 9 Japanese Laid-Open Patent Publication No. 2001-109154 [Patent Document 5] Japanese Patent Laid-Open Publication No. JP-A No. 2000-1101 [Patent Document 7] Japanese Patent Laid-Open Publication No. JP-A-2002-308866 (Patent Document No. JP-A-2002-308866) Japanese Unexamined Patent Application Publication No. JP-A No. Publication No. JP-A--------- SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art, and the object of the present invention is to provide excellent resolution, LWR is small, PEB temperature dependence is good, and pattern dumping characteristics are obtained. A pattern of excellent little defects, as a chemically amplified type of photoresist, is a useful linear composition of sensitive radiation. The inventors of the present invention have found that the above problems can be attained by using a polymer having a repeating unit having a specific structure and a repeating unit having an acid dissociable group, and the present invention has been accomplished. That is, the present invention provides the following sensitive radiation linear composition. [1] Containing a repeating unit (1) represented by the following general formula (1-1), a repeating unit (2) represented by the following general formula (1-2), and a repeating unit having an acid dissociable group (3) A linear composition of the sensitive radiation of the polymer (A) and the sensitive radiation linear acid generator (B). 【化1】

(1-1)

HN ) 〇 2 R3 (1-2) 200923579 In the above general formulae (1-1) and (1-2), R1 independently represents a hydrogen atom, a methyl group or a trifluoromethyl group. In the above general formula (1 - 0, R2 represents a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an alkylcarbonyl group having 1 to 12 carbon atoms, or a hydroxyalkyl group. In 1_2), X represents a single bond, a methyl group, a linear or branched alkyl group having a carbon number of 2 to 20, or a divalent cyclic hydrocarbon group having a carbon number of 3 to 9, and R3 represents at least one fluorine. a linear or branched alkyl group having 1 to 10 carbon atoms or an alicyclic alkyl group having 3 to 1 carbon atoms. [2] The above-mentioned radiation sensitive linear acid generator (b) contains the following general The linear composition of the radiation of the above-mentioned [1] of the compound represented by the formula (2).

(2) In the above general formula (2), R4 represents a hydrogen atom, a fluorine atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched carbon number of 1 to 10. An alkoxy group or a linear or branched oxycarbonyl group having a carbon number of 2 to 11, and R5 represents a linear or branched alkyl group having 1 to 10 carbon atoms and a linear chain having 1 to 10 carbon atoms. Or a branched alkoxy group, or a linear, branched or cyclic alkanesulfonyl group having a carbon number of 2 to 1, and R6 each independently represents a carbon number of 1 to h ^ -g. _ L chain a substituted or unsubstituted base group, or a +n-substituted or unsubstituted naphthyl group, or a two-R6-substituted or unsubstituted divalent group. k represents an integer of 〇~2, r is not an integer of 〇1, and X represents any of the following general formulas (3) to (6) (but, χ• is the following general anion, two A substituted or unsubstituted divalent group having a carbon number of 2 to 10 is formed by the combination of

0 R7—CnF2n-S^〇' II U 0 (3) A fluorine atom or an integer of carbon ~Μ. The alkylcarbonyl group of 1-6 is described in the general formula (3), R7 represents a substituted or unsubstituted hydrocarbon group having 1 to 12 hydrogen atoms, and n represents further. In the general formula (4), R8 represents a carbon number group. A hydrocarbon group having a carbon number of 12 or less substituted with an alkylcarbonyloxy group or a hydroxyalkyl group or unsubstituted. Further, in the above general formulas (5) and (6), 'R each independently represents a carbon number 丨~" linear or branched-shaped hospital group containing fluorine atoms, or two R9s are combined a substituted or unsubstituted divalent group having a fluorine atom of 2 to 1 Å. The linear composition of the radiation of the present invention is excellent in dissolvability, LWR is small, and temperature dependence of PEB is good, and Type tilting 200923579 The effect of the pattern of excellent 'very few defects'. When the effect is exerted, the linear composition of the sensitive radiation of the present invention can be used as a chemically amplified type of photoresist. MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the invention is described below, but the invention is not limited to the embodiment described below. That is, the general knowledge based on the trader's can be implemented as follows without departing from the scope of the invention. It is to be understood that the scope of the present invention is appropriately changed, improved, etc. Further, in the present specification, a radical (atomic group) which does not describe "substituted" and "unsubstituted" means that there is no substitution. Base The group (atomic group) and the group having a substituent (atomic group) 2 are all included in the present invention. For example, "hospital base" means not only a hospital base (unsubstituted base) which does not have a substituent, but also an alkyl group having a substituent (substituted alkyl group). I-sensitive radiation linear composition The sensitive radiation of the present invention is linearly composed of a sensitive radiation linear acid generator (B) (B)"). The system contains a polymer (A), and (hereinafter also referred to as "acid generator 1 polymer (A) (1), a repeating unit represented by a constituent component, and an acid-soluble polymer (A) having a general formula (ΐι) ' ), repeating unit shown in general formula (1-2) (2 -9- 200923579

ο In the general formulae (1-1) and (1-2), R1 independently represents a hydrogen atom, a methyl group, or a trifluoromethyl group. In the general formula (1-1), R2 represents a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an alkylcarbonyl group having 1 to 12 carbon atoms, or a hydroxyalkyl group. In the general formula (1-2), X represents a single bond, a methyl group, a linear or branched alkyl group having a carbon number of 2 to 20, or a divalent cyclic hydrocarbon group having a carbon number of 3 to 9, R3. It is a linear or branched alkyl group having at least one fluorine atom and having 1 to 10 carbon atoms, or an alicyclic alkyl group having 3 to 10 carbon atoms. (i) Repeating unit (1) A specific example of a linear or branched alkyl group or a cycloalkyl group having a carbon number of 1 to 12 in the 'group represented by R2' in the general formula (1-1), which may be mentioned Methyl, ethyl, propyl, isopropyl, isobutyl, t-butyl, cyclohexyl, cyclopentyl, cycloheptyl and the like. Further, specific examples of the alkylcarbonyl group and the hydroxyalkyl group having 1 to 12 carbon atoms include a methylcarbonyl group, an ethylcarbonyl group, a propyl mineral group, a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group. Among them, the methyl group, the ethyl group, the methylcarbonyl group, the ethylcarbonyl group, the hydroxymethyl group or the hydroxyethyl group represented by R2 in the formula (1-1) in general -10-200923579 are preferred. The polymer (A) is preferably one or more than two or more repeating units (1). Preferable specific examples of the monomer (radical polymerizable monomer) used in the production of the polymer (A) containing the repeating unit (1) include a general formula (1 · 1 - 1 ) to (1 - 1 -6 ) the compound shown. Further, in the general formulae (1-1-1) to (1-1-6), R1 represents a hydrogen atom, a methyl group or a trifluoromethyl group. 【化5】

-11 - 200923579 (ii) Repeating unit (2) As the X in the general formula (1-2), a linear or branched alkyl group having a methyl group and a carbon number of 2 to 20, a carbon number of 3~ A divalent cyclic hydrocarbon group of 9 is preferred. Further, in the above, a divalent cyclic hydrocarbon group, a linear alkylene group, an alkylene glycol group or an alkylene ester group is preferred. Preferred examples of X in the general formula (1-2) include a methyl group, an ethyl group, a 1,2-propyl group, a 1,3-propyl group, a tetramethyl group, and a five-extension group. Base, hexamethyl, heptamethyl, octamethyl, hexamethyl, decylmethyl, eleven methyl, decylmethyl, thirteen methyl, tetramethyl , fifteen stretch methyl, sixteen methyl, seventeen methyl, eighteen methyl, nineteen methyl, 1-methyl-1,3-propyl, 2-methyl-1 , 3-propyl, 2-methyl-1,2-propenyl, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, ethylene, a chain hydrocarbon group such as a propylene group or a 2-propylene group; a cyclopentene group such as a 1,3-cyclobutylene group; a cyclopentyl group such as a 1,3-cyclopentyl group; a 1,4-cyclohexyl group; a monocyclic hydrocarbon ring group such as a cyclohexyl group; an extended base; a crosslinked cyclic hydrocarbon ring group; Specific examples of the monocyclic hydrocarbon ring group include a cyclic alkyl group having 3 to 10 carbon atoms. Further, specific examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclodextyl group such as a 1,5-cyclodecyl group. Further, as a specific example of the original base of the spinosa, 1,4-extended base, 2,5-extended base. Further, specific examples of the crosslinked cyclic hydrocarbon ring group include a hydrocarbon ring group having 2 to 4 ring carbon numbers of 4 to 30. Further, examples of the hydrocarbon ring group having a carbon number of 4 to 3 of 2 to 4 ring atoms include an adamantane group such as a 1,5-adamantyl group or a 2,6-adamantyl group. -12- 200923579 As R3 in the general formula (1-2), a trifluoromethyl group is preferred. It is also preferred that the polymer (A) contains one or more than two or more repeating units (2). A preferred example of the monomer (radical polymerizable monomer) used in the production of the polymer (A) containing the repeating unit (2) is (((trifluoromethyl)sulfonyl)amine) Ethyl-1-methyl acrylate, 2·(((trifluoromethyl)sulfonyl)amino)ethyl-bu acrylate' and formula (1-2-1)~(1-2_6 ) the compound shown.

(1-2-1) (1-2-2) (1-2-3) (1-2-4)

^bC/vNHS02CF3 /^tv^NHS02CF3 (1-2-5) (1-2-6) (ΐϋ) Repeating unit (3) The polymer (A) is a repeating unit containing an acid-dissociable group (3). The "acid dissociable group" is a group which can be dissociated by the action of an acid. -13- 200923579 Therefore, the poly(fluorene) containing the repeating unit (3) having the "acid dissociable group" is a polymer which is capable of dissociating the acid dissociable group and having a property of solubility. The acid dissociable group is, for example, a group having a structure represented by the formula (7) or a t-butoxycarbonyl group. 【化7

(7) In the general formula (7), rig independently represents a monovalent alicyclic cigarette group of 1 to 2 碳, _ _ _ 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 a linear or branched scooped toffee group (however, at least one of R1G is a monovalent alicyclic L group having a carbon number of 4 to 20 or a derivative thereof), or any two R1Q are bonded to each other to form a carbon number of 4 a 20-valent alicyclic hydrocarbon group or a derivative thereof, and the remaining one R1G represents a monovalent alicyclic hydrocarbon group having a carbon number of 4 to 20 or a derivative thereof, or a linear or branched carbon number of 1 to 4 Alkyl. In the group represented by R1❶ in the general formula (7), examples of the monovalent or divalent alicyclic hydrocarbon group having 4 to 2 carbon atoms include cyclobutane, cyclopentane, cyclohexyl, and cycloglycan. a cycloalkane such as an alkane or a cyclooctane; an alicyclic ring such as a raw spinane, a tricyclodecane, a tetracyclododecane or an adamantane; and a group formed by the alicyclic ring; Base, ethyl, η-propyl, 丨-propyl, n-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, etc., linear, branched, branched A group substituted with a cyclic or cyclic alkyl group. They also have a carbon number based on the original spinane, tricyclic 癸-14 - 200923579 alkane, tetracyclododecane, adamantane, cyclopentane, or cyclohexane, or their alicyclic rings. A group substituted with a linear, branched or cyclic alkyl group of 1 to 4 is preferred. In the group represented by R1() in the general formula (7), as a derivative of a monovalent or divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, for example, a hydroxyl group; a carboxyl group; an oxo group (i.e., = mercapto group) is used. ); hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3- a hydroxyalkyl group having 1 to 4 carbon atoms such as hydroxybutyl or 4-hydroxybutyl; methoxy, ethoxy, η-propoxy, i-propoxy, n-butoxy, 2-methyl Propyloxy 1-methylpropoxy, t-butoxy, etc., having a carbon number of 1 to 4; cyano; cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, 4-chlorobutyl A compound having a carbon number of 4 to 20 or a divalent alicyclic hydrocarbon group substituted with a substituent of 2 to 5 or more. Among them, a compound in which a monovalent or divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms is substituted with a hydroxyl group, a carboxyl group, a hydroxymethyl group, a decyl group or a cyanomethyl group is preferred. In the group represented by RG in the general formula (7), a linear or branched alkyl group having a carbon number is, for example, a methyl group, an ethyl group, an n-propyl group, a propyl group, a η-butyl group, or a 2-methyl group. Propyl, 丨-methylpropyl, t-butyl and the like. Among them, methyl, ethyl, n-propyl and i-propyl are also preferred. In other words, as the repeating unit (3), any one of the general formula (1 - 3 - 1 ) to the group having a structure represented by the repeating formula represented by the general formula (7) 1 - 3 - 4 ) may be mentioned. example. -15 - 200923579

In the general formula (1-3-1) to (1-3-4), R1 independently represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and Rlf1 independently represents a linear or branched carbon number of 1 to 4. Alkyl group. Further, in the general formula (1-3-3), η represents an integer of 1 to 5. In the RI (> group represented by the general formula (1-3-1) to (1-3-4), a linear or branched alkyl group having a carbon number of 1 to 4, for example, a methyl group, Ethyl, η-propyl, i-propyl, η-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, etc. Among them, methyl, ethyl, η It is more preferable when the propyl group and the i-propyl group are used. When the acid dissociable group is a group represented by the general formula (1-3-2), it is particularly preferable that the two R1C) are simultaneously methyl groups. When the acid-dissociable group is a group represented by the general formula (1-3-3), η is an integer of 1 or 2, and it is particularly preferable when R1() is a methyl group or an ethyl group. When the acid dissociable group is a group represented by the general formula (1-3-4), it is particularly preferable that the two R1C) are simultaneously a methyl group. Further, as a repeating unit of -16 to 200923579 having a group having a structure represented by the general formula (7), a repeating unit represented by the general formula (1-3-5) to (1-3-12) is also preferable. 【化9】

(1-3-5) (1-3-6) (1-3-7) (1-3-8)

(1-3-9) (1-3-10) (1-3-11) (1-3-12) As a monomer used in the manufacture of a polymer (A) containing a repeating unit (3) (free Preferred specific examples of the base polymerizable monomer include 2-methyladamantyl-2-yl (meth)acrylate and 2-methyl-3-(meth)acryl-17-200923579 acid. Hydroxyadamantan-2-yl ester, 2-ethyladamantyl-2-yl (meth)acrylate, 2-ethyl-3-hydroxyadamantyl-2-yl (meth)acrylate, 2-n-propyladamantyl-2-yl (meth)acrylate, 2-isopropylidenyl-2-yl (meth)acrylate, 2-methylbicyclo(methyl)acrylate [2.2.1] Heptan-2-yl ester, (meth)acrylic acid-2-ethylbicyclo[2.2.1]heptan-2-yl ester, (meth)acrylic acid-8-methyltricyclo[ 5·2· 1.02'6]decane-8-yl ester, (meth)acrylic acid-8-ethyltricyclo [5.2.1.02'6]nonane-8-yl ester, (meth)acrylic acid-4 -Methyltetracyclo[6_2·1_13'6.02'7]dodecyl-4-yl ester, (meth)acrylic acid 4-ethyltetracyclo[6.2.1_13,6.02,7]dodecane- 4-yl ester, (meth)acrylic acid 1 (Bicyclo[2.2.1]heptan-2-yl)-1-methylethyl ester, 1-(tricyclo[5.2.1.02,6]decane-8-yl)-1-(meth)acrylate Methyl ethyl ester, 1-(tetracycline [6·2·1·13'6·02'7] dodec-4-yl)-1-methylethyl (meth)acrylate, (A) 1-(adamantan-1-yl)-1-methylethyl acrylate, 1-(adamantan-1-yl)-1-ethylethyl (meth)acrylate, (methyl) 1-(adamantan-1-yl)-1-methylpropyl acrylate, 1-(adamantan-1-yl)-1-ethylpropyl (meth)acrylate, (meth)acrylic acid 1 -(3-hydroxyadamantan-1-yl)-1 -methylethyl ester, 1,1 -dicyclohexylethyl (meth)acrylate, 1,1-di(bicyclo) 2.2.1] Heptane-2-yl)ethyl ester, 1,1-di(tricyclo[5·2_1.02'6]nonane-8-yl)ethyl (meth)acrylate, (A) 1,1-di(tetracyclo[6.2.1.13'6.02'7]dodecan-4-yl)ethyl acrylate, 1,1 -di(adamantan-1-yl)(meth)acrylate Ethyl ester, (methyl) propyl-18- 200923579 enoic acid 1-methyl-1-ring Base ester, 1-ethyl-1-cyclopentyl (meth)acrylate, 1-isopropyl-1-cyclopentyl (meth)acrylate, 1-methyl-1-(meth)acrylate Cyclohexyl ester, 1-ethyl-1-cyclohexyl (meth)acrylate, 1-isopropyl-1-cyclohexyl (meth)acrylate, 1-methyl-1-cyclo(meth)acrylate Heptyl ester, 1-ethyl-1-cycloheptyl (meth)acrylate, 1-isopropyl-1-cycloheptyl (meth)acrylate, 1-methyl-1 (meth)acrylate - cyclooctyl ester, 1-ethyl-1-cyclooctyl (meth)acrylate, 1-isopropyl-1-cyclooctyl (meth)acrylate, and the like. They also use 2-methyladamantyl-2-yl (meth)acrylate, 2-ethyladamantyl-2-yl (meth)acrylate, and (meth)acrylic acid-2- Methyl bicyclo[2.2.1]heptan-2-yl ester, (meth)acrylic acid-2-ethylbicyclo[2.2.1]heptan-2-yl ester, (meth)acrylic acid 1-(bicyclo[ 2.2.1]heptan-2-yl)-1-methylethyl ester, 1-(adamantan-1-yl)-1-methylethyl (meth)acrylate, (meth)acrylic acid 1 -Methyl-1-cyclopentyl ester '1-ethyl-1-cyclopentyl (meth)acrylate, 1-methyl-1-cyclohexyl (meth)acrylate, (meth)acrylic acid 1 Ethyl-1-cyclohexyl ester is preferred. (iv) Other repeating units The polymer (A) may also be a repeating unit (hereinafter also referred to as "other repeating unit") containing one or more repeating units (1) to (3). As a preferred example of the "other repeating unit", there are a repeating unit represented by the general formula () to (1-4-6) (hereinafter also referred to as "repetitive unit (4)"), and a general formula (1 - 5). Repeat units (hereinafter also referred to as -19-200923579 as "repeating units (5)"), repeating units shown in general formula (1 - 6) (hereinafter also referred to as "repetitive units (6)"), and general formula ( 1 -7 ) The repeating unit shown below (also referred to as "repeating unit (7)"). It is preferred that the polymer (A) contains at least one of these repeating units. [10

»11 generation · generation 1 :0

〇

〇 (1-4-1) (1-4-2) m Ό (1-4-3)

>12,0(1-4-4)

0

In the general formulae (1-4-1) to (1-4-6), R1 independently represents a hydrogen atom, a methyl group or a trifluoromethyl group. In the general formula (1-4-1), R11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent, and 1 represents an integer of 1 to -20 to 200923579 3 . In the general formula (1-4-4), R12 represents a hydrogen atom or a methoxy group. In the general formulae (1-4-2) and (1-4-3), A represents a single bond or a methyl group, and m represents 0 or 1. In the general formulae (1-4-3) and (1-4-5), B represents an oxygen atom or a methyl group.

In the general formula (1-5), R1 represents a hydrogen atom, a methyl group or a trifluoromethyl group, and X represents a polycyclic alicyclic hydrocarbon group having 7 to 20 carbon atoms. [Chem. 1 2]. Bu. >13 f3c^( HO CF3 (1-6) In the general formula (1-6), R1 represents a hydrogen atom, a carbon number of 1 to 4, a trifluoromethyl group, or a hydroxymethyl group, and R13 represents a divalent value. Chain or cyclic hydrocarbon group, alkanediol group, or alkyl ester group. -21 - 200923579 [Chem. 1 3]

(1-7) In the general formula (1-7), R1 represents a hydrogen atom or a methyl group, and X represents a single bond or a divalent organic group having 1 to 3 carbon atoms, and Y independently represents a single bond or a carbon number. a divalent organic group of 1 to 3, and R14 independently represents a hydrogen atom, a hydroxyl group, a cyano group, or a COOR15 group (however, R15 represents a hydrogen atom, a linear or branched carbon group having 1 to 4 carbon atoms, or carbon) Number 3 to 20 of an alicyclic alkyl group). (Repeating unit (4)) Preferred examples of the monomer (radical polymerizable monomer) used for producing the polymer (A) containing the repeating unit (4) include (meth)acrylic acid-5. -oxo-4-oxo-tricyclo[4.2.1.03'7]non-2-yl ester, (meth)acrylic acid-9-methoxycarbonyl-5-oxo-4-oxo-tricyclo[4.2 .1. 03'7]Indol-2-yl ester, (meth)acrylic acid-5-oxo-4-oxo-tricyclo[5.2.1.03'8]non-2-yl ester, (meth)acrylic acid -10-methoxycarbonyl-5-oxo-4-oxo-tricyclo[5_2.1.03'8]non-2-yl ester, (meth)acrylic acid-6-oxo-7-oxo-bicyclo[ 3.2. 1] Oct-2-yl ester, (meth)acrylic acid 4-methoxycarbonyl-6-oxo-7-oxa-bicyclo[3.2.1]octyl--22- 200923579 2-based ester, (meth)acrylic acid-7-oxo-8-oxo-bicyclo[3.3.1]indole-2-yl ester, (meth)acrylic acid-4-methoxycarbonyl-7-oxo-8-oxa- Bicyclo[3.3.1]non-2-yl ester, 2-oxotetrahydropyran-4-yl (meth)acrylate, 4-methyl-2-oxotetrahydro(meth)acrylate Pyran-4-yl ester, 4-ethyl-2-oxotetrahydropyridyl (meth)acrylate喃-4-yl ester, 4-propyl-2-oxotetrahydropyran-4-yl (meth)acrylate, 2-oxotetrahydrofuran-4-yl (meth)acrylate, ( 5-(Oxotetrahydrofuran-3-yl)methyl (meth)acrylate, 3,3-dimethyl-2-oxotetrahydrofuran-4-yl (meth)acrylate, (meth)acrylic acid-2,2 - dimethyl-5-oxotetrahydrofuran-3-yl ester, (meth)acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-3-yl ester, (meth)acrylic acid-2-oxyl Tetrahydrofuran-3-yl ester, (meth)acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran-3-yl ester, (meth)acrylic acid-5,5-dimethyl-2-oxo Tetrahydrofuran-3-yl ester,-5,5-dimethyl-2-oxotetrahydrofuran-4-yl (meth)acrylate, 5-oxotetrahydrofuran-2-ylmethyl (meth)acrylate Ester, (meth)acrylic acid-3,3-dimethyl-5-oxotetrahydrofuran-2-ylmethyl ester, (meth)acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-2 -ylmethyl ester and the like. (Repeating unit (5)) In the general formula (1-5), a preferred example of the polycyclic alicyclic hydrocarbon group having 7 to 20 carbon atoms represented by X is a bicyclo[2.2.1] heptane or a bicyclic ring. [2_2.2] Cyclohexane of trioctane [5.2.1.02'6] decane, tetracyclo[6_2.1_13'6.02'7]dodecane, tricyclo[3.3.1.1'7]nonane a hydrocarbon group such as an alicyclic ring. Further, these alicyclic rings may also be those having a substituent. Specific examples of the substituent include methyl group, ethyl-23-200923579 IX-propyl group, butyl group (tetra), benzyl group, η-butyl group, 2-methyl group, and propyl group-number of fires 1 to 4. In addition to the specific examples of the substituent in the linear 'branched or cyclic alkyl group, for example, a cyano group such as a thiol group, a hydroxyalkyl group having a carbon number of 1 to 1 fluorene, or a substituent such as a carboxyl group may be used. . Preferred examples of the monomer (radical polymerizable monomer) used for producing the polymer (Α) containing the repeating unit (5) include (meth)acrylic acid-bicyclo[m]heptyl group. Vinegar, (meth)acrylic acid monocyclohexyl ester '(meth)acrylic acid-bicyclo[4.4.〇] vinegar, (meth)acrylic acid-bicyclo[2.2.2]octyl ester, (meth)acrylic acid Tricyclo [5.2.1.02'6] decyl ester, (meth)acrylic acid tetracyclo[6.2.1.13,6'02'7]dodecyl ester, (meth)acrylic acid-tricyclo[3.3.1.I3 , 7] oxime ester and the like. (Repeating unit (6)) In the general formula (1_6), specific examples of the divalent chain-like or cyclic hydrocarbon group represented by Rl3 include a methyl group, an ethyl group, and a propyl group (1, 3). _ 芮 芮 or 1,2- propyl, etc.), tetramethyl, pentamethyl, hexamethyl, hexamethylene, octamethyl, hexamethylene, decylmethyl, ^--Extension Methyl, Twelve Methyl, Thirteen Methyl, Fourteen Methyl, Fifteen Ket, Sixteen Methyl, Seventeen Methyl, Eighteen Methyl, Ten Nine-methyl thiol, 1-methyl-1,3-propanyl, 2-methyl-1,3-propanyl, methyl-1,2-propyl, 1-methyl- I,4-butylene, 2·methyl-I,4-dibutyl 2, ethylene, propylene, 2-propylene, etc. chain hydrocarbon group; 1,3-cyclobutylene-based Cyclopentyl group, 1,3_cyclopentyl group, pentyl group, 1,4_ γ, cyclohexyl group, hexyl group, and 1,5-cyclodextyl group π -24- 200923579 A monocyclic hydrocarbon ring group such as a cycloalkyl group having a carbon number of 3 to 1 fluorene; 14 - an exogenous spinach base and a 2,5-extended base 5_extended alkane, 2,6-stretch Rigid groups based hospital firing extending adamantyl group ~ 4 carbon atoms, cyclic hydrocarbon ring group 4~30 crosslinked cyclic hydrocarbon ring group. Preferred examples of the monomer (radical polymerizable monomer) used for producing the polymer (A) having a repeating unit (6) include (meth)propionic acid (1,1,1- Difluoro-2-trifluoromethyl-2-carbyl-3-propyl) vinegar, (meth)propionic acid (trifluoro-2-trifluoromethyl-2-yl-4-yl) Vinegar, (meth)acrylic acid (丨, 1,1_trifluoro-2-trifluoromethyl-2-hydroxy-5-pentyl) ester (meth)acrylic acid (1,l5l•trifluoro- 2·Trifluoromethyl-2-hydroxy-4-pentyl)ester, 2-{[5-(1',1',1'-trifluoro-2'-trifluoromethyl-(meth)acrylate-(meth)acrylate 2'-hydroxy)propyl]bicyclo[2.2.1]heptyl}acetate, (methyl)propanic acid 4-{[ 9-( 1,,1,1,-trifluoro-2'-difluoro Methyl-2'-trans)propyl]tetracyclo[6_2.1_13'6.02'7] lauric acid ester. (Repeating unit (7)) In the general formula (1-7), specific examples of the divalent organic group having 1 to 3 carbon atoms represented by X and Y include methyl group, ethyl group and propyl group. Wait. Further, in the general formula (1-7), a specific example of a linear or branched alkyl group having 1 to 4 carbon atoms represented by R15 as a group represented by COOR>5 in the group represented by R14 is exemplified. Methyl, ethyl, η-propyl, i-propyl, n-butyl, 2-methylpropyl, methylpropyl, t-butyl, and the like. Further, specific examples of the alicyclic alkyl group having 3 to 20 carbon atoms are represented by "CnH^-" (n is an integer of 3 to 20), and examples thereof include a cyclopropyl group, a cyclobutyl group, and a ring. Cyclol, cyclohexa-25- 200923579, cycloheptyl, cyclooctyl and other cycloalkyl; bicyclo [2.2.1] heptyl, ~cyclo[5.2.1.〇2,6]decyl, tetracycline 6.2.1_13, 6.02'7] a polycyclic alicyclic alkyl group such as a ruthenium, an adamantyl group; or a cycloalkyl group or a polycyclic ring of one or more alkyl groups which are linear, branched or precipitated The substituent of the alicyclic alkyl group is substituted. Further, at least one of the three R14 in the general formula (1-7) is a non-hydrogen atom, and when X is a single bond, it is preferable that at least one of the three Ys is a divalent organic group having 1 to 3 carbon atoms. . Preferred examples of the monomer (radical polymerizable monomer) used for producing the polymer (A) having a repeating unit (7) include 3-hydroxyadamantane-1-yl (meth)acrylate. Ester, (meth)acrylic acid 3_ via adamant-1-ylmethyl ester, (meth)acrylic acid 3,5-dihydroxyadamantan-1 -yl ester, (meth)acrylic acid 3,5 - two Hydroxyadamantane-1-ylmethyl ester, 3-hydroxy-5-methyladamantan-1-yl (meth)acrylate, 3,5-dihydroxy-7-methyladamantane (meth)acrylate -1-yl ester, 3-hydroxy-5,7-dimethyladamantan-1-yl (meth)acrylate, 3-hydroxy-5,7-dimethyladamantane-1 (meth)acrylate -ylmethyl ester and the like. (v) Further repeating unit polymer (A) may be a repeating unit other than one or more repeating units (1) to (3) and repeating units (4) to (7) (hereinafter also referred to as "further Other repeating units"). As a further preferred example of the other repeating unit, there are a repeating unit formed by the cleavage of the polymerizable unsaturated bond of the polyfunctional monomer. Specific examples of such a polyfunctional monomer include (meth)acrylate having a bridged hydrocarbon skeleton such as dicyclopentenyl (meth)acrylate or adamantyl (meth)acrylate. 26-200923579; unsaturated carboxylic acid such as carboxyprofenyl (meth) acrylate, decyl sulfonate (meth) decanoate, trimethyl sulfonate, (methyl) propyl sulfonate An ester containing a hydroxyl group having a bridged hydrocarbon skeleton; methyl (meth)propionate, c methyl)propyl acetoacetate η-propyl (meth)acrylate, (meth) propyl _ acid η-butyl ester, (methyl) acrylic acid 2-methyl propyl vinegar, 1-methyl propyl (meth) acrylate, (methyl) propylene acid t-butyl vinegar, (meth) propylene Acid 2 - base ethyl vinegar, 2-hydroxypropyl (meth) acrylate, 3- propyl propyl (meth) acrylate, cyclopropyl propyl (meth) acrylate, (meth) acrylate ring Amyl ester, cyclohexyl (meth)acrylate, 4-methoxycyclohexyl (meth)propanoate, 2-cyclopentyloxyacetate (meth)acrylate, (methyl)propane Acid 2-cyclohexyloxycarbonyl B Ester '(methyl)acrylic acid 2_(4-methoxycyclohexyl)hydroxycarbonylethyl ester, etc. (meth)propionic acid esters without bridged hydrocarbon skeleton; α-hydroxymethyl methacrylate 'α-hydroxyethyl methacrylate, α-methyl methacrylate η-propyl ester, α-transmethyl methacrylate η· butyl and the like α-hydroxy methacrylate; (methyl An unsaturated nitrile compound such as acrylonitrile, α·chloroacrylonitrile, butenenitrile, maleonitrile, fuamonitrile, methyl methacrylonitrile, methyl methacrylonitrile or itacononitrile; ) acrylamide, hydrazine, hydrazine-dimethyl (meth) acrylamide, crotonamide 'maleamide, fumarine, mesaconamine, cimolamide, itaconamide, etc. a saturated guanamine compound; a ruthenium-(meth) propylene hydrazinomorph, a ruthenium-ethylene-ε-caprolactam, a fluorene-vinylpyrrolidone, a vinylpyridine, a -27-200923579 vinylidene compound such as a vinyl imidazole; An unsaturated carboxylic acid (anhydride) such as acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; ) 2-carboxyethyl acrylate, 2-carboxypropyl (meth)acrylate, 3-carboxypropyl (meth)acrylate, 4-carboxybutyl (meth)acrylate, 4-carboxyl (meth)acrylate a carboxyl group-containing ester having a bridged hydrocarbon skeleton having no unsaturated carboxylic acid such as hexyl ester; I, 2-adamantanediol di(meth)acrylate '1,3-adamantanediol di(methyl) a polyfunctional monomer having a bridged hydrocarbon skeleton, such as acrylate, 1,4-adamantanediol di(meth)acrylate, tricyclodecyldimethylol di(meth)acrylate; Glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2,5- Dimethyl-2,5-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-decanediol di(meth)acrylic acid Ester, 1,4-bis(2-hydroxypropyl)benzenedi(meth)acrylate, 1,3-bis(2-hydroxypropyl)benzenedi(meth)acrylate, etc. More skeleton Functional monomer and the like. (2) The ratio of the content of each repeating unit to the repeating unit (1) of the polymer (A) (content ratio) is generally 1 〇 to 90 mol%, preferably 20 to 80 mol%, for the total repeating unit. More preferably, it is 30 to 70 mol%. When the content of the repeating unit (1) is less than 10 m ο 1 %, the developing property as a photoresist may be lowered by -28-200923579. Moreover, the pattern formed has a tendency to be prone to defects. On the other hand, when it exceeds 90 mol%, the resolution of the photoresist, the LWR, and the PEB temperature dependency tend to decrease. The ratio (content ratio) of the repeating unit (2) contained in the polymer (A) is usually 5 to 60 mol%, preferably 5 to 50 mol%, more preferably 10 to 40 mol%, based on the total repeat unit. When the content of the repeating unit (2) is less than 5 mol%, the LWR as a resist and the pattern pour resistance tend to be lowered. Moreover, the pattern formed has a tendency to be prone to defects. On the other hand, when it exceeds 60 mol%, the resolution as a photoresist tends to be lowered. The ratio (content ratio) of the repeating unit (3) contained in the polymer (A) is usually 10 to 90 mol%, preferably 10 to 80 mol%, more preferably 20 to 80 mol%, based on the total repeat unit. When the content of the repeating unit (3) is less than 10 mol%, the resolution of the photoresist, the LWR, and the PEB temperature dependence tend to deteriorate. On the other hand, when it exceeds 90 m〇l%, the developability as a photoresist tends to be lowered. Moreover, the pattern formed tends to be prone to defects. The ratio (content ratio) of the repeating unit (4) contained in the polymer (A) is usually 10 to 70 mol%, preferably 15 to 65 mol%, more preferably 20 to 60 mol%, based on the total repeat unit. When the content of the repeating unit (4) is less than 1 mol%, the developing property as a photoresist may be lowered. On the other hand, when it exceeds 70 mol%, the solubility of the photoresist solvent tends to decrease, and the resolution tends to decrease. The ratio of the repeating unit (5) contained in the polymer (A) (containing the ratio of -29 to 200923579) is generally 30 m〇i% or less, preferably 25 mol% or less, for the total repeat unit. When the content of the repeating unit (5) exceeds 30 mol%, the resist film tends to swell by the alkaline developing solution, or the developing property as a resist tends to be lowered. The ratio (content ratio) of the repeating unit (6) contained in the polymer (A) is generally 30 m〇l% or less in terms of the total repeat unit, and is preferably 2 5 m ο 1 % or less. When the content of the repeating unit (6) exceeds 30 m ο 1 %, there is a tendency that the resist pattern top loss occurs and the pattern shape deteriorates. The ratio (content ratio) of the repeating unit (7) contained in the polymer (A) is usually 30% by mole or less, preferably 25 % by mole or less, based on the total repeating unit. When the content of the repeating unit (7) exceeds 30 mol%, the resist film tends to swell by the alkaline developing solution, or the developing property as a photoresist tends to be lowered. Further, the ratio (content ratio) of "other repeating units" contained in the polymer (A) is generally 50 m ο 1 % or less, preferably 4 0 m ο 1 % or less for the total repeat unit. . (3) Physical properties The polystyrene-ethyl equivalent weight average molecular weight (hereinafter also referred to as "Mw") calculated from gel permeation chromatography (hereinafter also referred to as "GPC") of the polymer (A) is not It is particularly limited, preferably from 1000 to 100,000', more preferably from 1,000 to 30,000, and particularly preferably from 20,000 to 20,000. When the Mw of the polymer (A) is less than 1 〇 〇 ’, the heat resistance as a photoresist may be lowered. On the other hand, when it exceeds 100 〇 ’, the development performance as a photoresist may be lowered. -30- 200923579 The ratio of the Mw of the polymer (A) to the number average molecular weight (hereinafter also referred to as "Mn") in terms of polystyrene ethyl group by GPC (Mw/Mn; dispersity (molecular weight distribution)) It is preferably 5. to 3.0, more preferably 1.0 to 2.0. Further, when the radiation sensitive linear composition of the embodiment of the present invention is prepared, only one type of polymer (A)' may be used, but it is preferred to combine two or more types of the polymer (A). (4) Manufacturing method The polymer (A) can be synthesized by a usual method such as radical polymerization. Specifically, a method in which a reaction solution containing each monomer and a radical initiator is dropped into a reaction solution containing a reaction solvent or a monomer to carry out a polymerization reaction, or a reaction solution containing each monomer, It is synthesized by a method in which a reaction solution containing a radical initiator is separately dropped into a reaction solution containing a reaction solvent or a monomer to carry out polymerization. In other words, it is preferred to carry out the polymerization by separately dropping a reaction solution containing each monomer and a reaction solution containing a radical initiator into a reaction solution containing a reaction solvent or a monomer. The reaction temperature in the polymerization reaction can be appropriately set depending on the kind of the radical initiator, and is usually from 30 to 180 ° C, preferably from 40 to 160. (:, more preferably 50 to 140 ° C. The required time for dropping the reaction solution, etc.) can be appropriately set depending on the polymerization reaction temperature, the type of the radical initiator, the type of the monomer to be reacted, etc. 30 minutes to 8 hours' is preferably 4 5 minutes to 6 hours, more preferably 1 to 5 hours. Also, the total reaction time with the dropping time can be appropriately set, usually 30 minutes - 31 - 200923579 ~ 8 hours, preferably 4 5 minutes to 7 hours, more preferably 1 to 6 hours. When dropping in the reaction solution containing a monomer, the ratio of the monomer contained in the reaction solution dropped is used for the polymerization. The total monomer amount is preferably 30_1% or more, more preferably 50 mol% or more, and particularly preferably 70 mol% or more. Specific examples of the radical initiator are 2, 2'. - azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis (2 , 4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), :1,1'-azobis(cyclo) Hexane- 1-carbonitrile, 2,2'-azobis (2-A) Benzyl-N-phenylpropionamidine dihydrochloride, 2,2'-azobis(2-methyl-N-2-propenylpropionamidine) dihydrochloride, 2,2'-azobis [2-(5-Methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis{2-methyl-N-[ 1, bis(hydroxymethyl) 2-hydroxyethyl]propanolamine}, dimethyl-2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-(hydroxymethyl)propionitrile), etc. Further, these radical initiators may be used singly or in combination of two or more. The solvent used for the polymerization reaction may be dissolved. The monomer to be used is only a solvent which does not inhibit the polymerization reaction (for example, a solvent which inhibits polymerization such as nitrobenzene or a solvent which promotes chain transfer such as a hydrogenthio compound, etc.). As a specific example of the solvent, Examples thereof include alcohols, ethers, ketones, decylamines, esters and lactones, nitriles, and mixtures thereof. Specific examples of the alcohols include methanol, ethanol, propanol, and isopropanol. Butanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene Monoethyl ether, 1-methoxy--32-200923579 2-propanol. Specific examples of the ethers include propyl ether, diisopropyl ether, butyl methyl ether, tetrahydrofuran, 1,4-dioxane, and 1, 3 - dioxolane, 1,3 - dioxan, etc. Specific examples of the ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl isopropanone, and methyl isobutyl ketone. Specific examples of the amines include N,N-dimethylformamide, hydrazine, and hydrazine-dimethylacetamide. Specific examples of the esters and lactones include ethyl acetate 'acetate A Ester 'isobutyl acetate, γ-butyrolactone. Specific examples of the nitrile include acetonitrile, propionitrile, and nitrile. Further, these solvents may be used singly or in combination of two or more. After the end of the polymerization, the polymer (A) is preferably recovered by reprecipitation. That is, after the completion of the polymerization reaction, the reaction liquid is introduced into the reprecipitation solvent, and the intended polymer (A) is preferably recovered as a colloid. As a reprecipitation solvent, water, alcohols, ethers, ketones can be used. , guanamines, esters and lactones, nitriles, and mixtures thereof. Specific examples of the alcohol include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, and 1-methoxy-2-propanol. Specific examples of the ethers include propyl ether, isopropyl ether, butyl methyl ether 'tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, and 1,3-dioxane. Specific examples of the ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl isopropanone, and methyl isobutyl ketone. Specific examples of the guanamines include hydrazine, hydrazine-dimethylformamide, hydrazine, and hydrazine-dimethylacetamide. Specific examples of the ester and the lactone include ethyl acetate, methyl acetate, isobutyl acetate, and γ-butyrolactone. Specific examples of the nitrile include acetonitrile, propionitrile, and butyronitrile. The ratio of the low molecular weight component derived from the monomer contained in the polymer (A) is preferably 1.0% by mass of the polymer (A) in terms of solid content, and is preferably 0.1 to 33,23,579,579% by mass or less. When 〇·〇 is 7 mass% or less, it is more preferable, and when it is 0.05 mass% or less, it is particularly preferable. When the content ratio of the low molecular weight component is 〇_1% by mass or less, when the polymer (A) is used to form a photoresist film and then subjected to liquid immersion exposure, the amount of the dissolved material in contact with the water of the photoresist film can be reduced to not The extent to which exposure has an impact. Further, since the linear composition of the radiation containing the polymer (A) is extremely difficult to generate foreign matter during storage, coating unevenness is extremely difficult to occur at the time of coating, and the occurrence of defects at the time of formation of the photoresist pattern can be sufficiently suppressed. Specific examples of the low molecular weight component derived from the monomer include a monomer, a dimer, a trimer, an oligomer, and the like, and a component having a Mw of 500 or less. The component having a M w of 500 or less may be removed by, for example, chemical purification such as water washing or layered liquid extraction, or may be removed by a combination of these chemical purification methods and physical purification such as limiting filtration or centrifugation. Further, the ratio of the low molecular weight component contained in the polymer (A) can be quantified by analysis by high-speed liquid chromatography (HPLC). Further, the ratio of the halogen, metal or the like contained in the polymer (A) is preferably as small as possible. When the polymer (A) having a small content ratio of impurities is used, it is possible to provide a linear composition of sensitive radiation which is further improved in sensitivity, resolution, process stability, and pattern shape. (2) The radiation sensitive linear acid generator (B) The sensitive radiation linear acid generator (B) is a component which functions as a photoacid generator by the acid generated by exposure. By dissolving the acid generated by the acid generator (B), the acid dissociable group present in the polymer (A) contained in the linear composition of the sensitive radiation is dissociated (the protective group is detached) (A) becomes soluble alkaline. As a result, the exposed portion of the resist film is easily soluble in the alkaline developing solution, and a positive resist pattern is formed -34-200923579. Further, the sensitive radiation linear composition of the present invention may contain only one acid generator (B), but may contain two or more kinds of acid generators (B). (1) Component The compound represented by the general formula (2) (hereinafter also referred to as "acid generator (〗)") is preferred as the acid generator (B). [化1 4] R4

Γ

, S+-R6 R6 (2) In the general formula (2), R4 represents a hydrogen atom, a fluorine atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched carbon number of 1 to 10. Alkoxy group or a linear or branched oxycarbonyl group of R 2 to 1 1 R 5 represents a linear or branched group having a carbon number of 1 to 10, and a carbon number of 1 to 10 a linear or branched alkoxy group, or a linear, branched or cyclic alkanesulfonyl group having 2 to 1 carbon atoms, and r6 independently represents a linear or branched carbon number of 1 to 10. A substituted or unsubstituted divalent group having a carbon number of 2 to 10 formed by a combination of an alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group, or a combination of two & An integer of 0 to 2; r is an integer of 0 to 10 (preferably an integer of 〇~2), and an anion represented by any one of general formulas (3) to (6) (however, ·, ~ X is ~~~ -35- 200923579 In the general formula (3), the two R6s do not combine to form a substituted or unsubstituted divalent group having a carbon number of 2 to 10.

In the general formula (3), r7 represents a hydrogen atom, a fluorine atom, or a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and η represents an integer of 1 to 1 Å. Further, in the general formula (4), 'R8' represents an alkylcarbonyl group having an alkyl group of 丨6 or 6 or an alkylcarbonyloxy group, or a hydrocarbon group having 1 to 12 carbon atoms which is substituted with or substituted with an alkyl group. Further, in the general formulae (5) and (6), r9 independently represents a linear or branched alkyl group having a carbon number of 1 to 10, or a carbon number formed by combining two R9 groups. a substituted or unsubstituted divalent group of a fluorine atom of ～10. (i) Acid generator (1) In the general formula (2), a specific example of a linear or branched alkyl group having 1 to 10 carbon atoms in the group represented by R4 to R6 is a methyl group. Ethyl, η-propyl, i-propyl, η-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, η-pentyl, neopentyl, η-hexyl, Η-heptyl, η-semiyl, 2-ethylhexyl' η-fluorenyl, η-fluorenyl, and the like. Among them, methyl, ethyl, η-butyl and t-butyl are also preferred. -36- 200923579 In the general formula (2), in the group represented by R4 and R5, a specific example of a straight-chain or branched alkoxy group of f may be an oxo group, an η-propoxy group, or a fluorene-propyl group. Oxyl, n_yoxy, 2 1 methylpropoxy, t -butoxy, η-pentyloxy, neojj; yl, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy Base, decyloxy and the like. Among them, methoxy, ethoxy, and n-oxy are also preferred. In the general formula (2), a specific example of a carbon-bonded or branched alkoxycarbonyl group in the group represented by R4, a carbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, and an i-propoxy group Alkyl, 2-methylpropoxycarbonyl, 1-methylpropoxy | alkaloid, η-pentyloxycarbonyl, neopentyloxycarbonyl, ηheptyloxyindenyl, η-octyloxy Ore, 2-ethylhexanooxycarbonyl, η-decyloxycarbonyl, and the like. Among them, a methoxycarbonyl group and an η-butoxycarbonyl group are preferred. In the general formula (2), in the group represented by R5, the specific acid group, the ethylsulfonyl group, the η-propylsulfonyl group, and the η- which are carbon chain, branched or cyclic alkanesulfonyl groups. Butanesulfonate _ base ' η-pentanesulfonyl, neopentasulfonyl, η-hexylsulfonyl, η-octylsulfonyl, 2-ethylhexylsulfonyl, η-valvee | Cyclopentasulfonyl, cyclohexylsulfonyl and the like. The thiol sulfhydryl group, the η-propane sulfonyl group, the η-butylsulfonyl group, and the cyclohexyl fluorenyl group are preferred. In the general formula (2), in the group represented by R6, 'as ® 乍 is a carbon number of 1 to 1 G I methoxy 'ethyl-methylpropoxy, oxime; oxy, η-hexyloxy η-oxime a methoxycarbonyl group; a fluorenyl group, an η-butoxy-Scarbonyl group, a t-butoxy-hexyloxycarbonyl group, a ruthenium group, a ruthenium group η -壬1 oxycarbonyl, the number of 1 to 1 〇 straight 11 ' can be mentioned as methyl sulfonate ^, tert_ butyl sulfonyl, η - ng 醯 1 醯 base, η - sulfonium sulfonate also known as methyl sulfonate Phenylcyclopentasulfonyl, "substituted or unsubstituted -37-200923579 phenyl specific examples" can be exemplified by phenyl, fluorenyl-tolyl, m-tolyl, p-tolyl, 2,3-dimethicone Basic group '2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl' 3,4-dimethylphenyl, 3,5-dimethyl Phenyl, 2,4,6-dimethylphenyl, 4-ethylphenyl, 4-t-butylphenyl, 4-cyclohexylphenyl, 4-fluorophenyl, etc.; phenyl; The base is substituted with a phenyl group substituted with a linear, branched or cyclic alkyl group having a carbon number of 丨1 to 1 ;; and the phenyl or alkyl substituted phenyl group is at least one selected from the group consisting of a hydroxyl group and a carboxyl group. Cyano, nitro Alkoxy, alkoxyalkyl, alkoxycarbonyl group, alkoxy group and oxo group of the several groups of group substituted group. Among the examples in which the phenyl group and the alkyl-substituted phenyl group are substituted, examples of the alkoxy group include a methoxy group, an ethoxy group, a η-propoxy group, a fluorene-propoxy group, and a η-butyl group. a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms such as an oxy group, a 2-methylpropoxy group, a propylpropoxy group, a butyloxy group, a cyclopentyloxy group or a hexyloxy group. Wait. In the group in which a phenyl group and a group-substituted phenyl group may be substituted, a specific example of the alkoxyalkyl group is exemplified by methoxymethyl group, ethoxymethyl group, 丨-methoxyethyl group, and 2 a linear, branched or cyclic alkoxyalkyl group having a carbon number of 2 to 2 1 such as a methoxy group, a hydrazine-ethoxyethyl group or a 2 ethoxyethyl group. In the group in which a phenyl group and a substituted phenyl group may be substituted, specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxy fluorenyl group, and a 1-propoxy group. Base group, η·butoxycarbonyl group, 2-methylpropoxyfluorenyl group, 1-methylpropoxycarbonyl group, butyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbyl group, etc. A linear, branched or cyclic alkoxycarbonyl group having 2 to 21 carbon atoms. -38- 200923579 In the group in which a phenyl group and an alkyl-substituted phenyl group may be substituted, specific examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, and a η- Propyloxycarbonyloxy, i-propoxycarbonyloxy, η-butoxycarbonyloxy, t-butoxycarbonyloxy, cyclopentyloxycarbonyloxy, cyclohexyloxycarbonyloxy, etc. A linear, branched or cyclic alkoxycarbonyloxy group having 2 to 2 carbon atoms. In the general formula (2), preferred examples of the substituted or unsubstituted phenyl group represented by R6 include a phenyl group, a 4-cyclohexylphenyl group, a 4-t-butylphenyl group, and a 4-methoxybenzene group. Base, 4-t-butoxyphenyl, and the like. In the general formula (2), examples of the substituted or unsubstituted naphthyl group in the group represented by R6 include 1-naphthyl group, 2-methyl-1-naphthyl group, and 3-methyl-1- Naphthyl, 4-methyl-1-naphthyl, 5-methyl-1-naphthyl, 6-methyl-1-naphthyl, 7-methyl-1-naphthyl, 8-methyl-1- Naphthyl, 2,3-dimethyl-1-naphthyl, 2,4-dimethyl-1-naphthyl, 2,5-dimethyl-1-naphthyl, 2,6-dimethyl- 1-naphthyl, 2,7-dimethyl-1-naphthyl, 2,8-dimethyl-1-naphthyl, 3,4-dimethyl-1-naphthyl, 3,5-dimethyl 1-naphthyl, 3,6-dimethyl-1-naphthyl, 3,7-dimethyl-1-naphthyl, 3,8-dimethyl-1-naphthyl, 4,5- Dimethyl-1-naphthyl, 5,8-dimethyl-1-naphthyl, 4-ethyl-1-naphthyl, 2-naphthyl, 1-methyl-2-naphthyl, 3- a naphthyl group such as methyl-2-naphthyl or 4-methyl-2-naphthyl; an alkyl group in which the naphthyl group is substituted by a linear, branched or cyclic alkyl group having 1 to 1 carbonium. Substituted naphthyl; these naphthyl or alkyl substituted naphthyl groups are at least one selected from the group consisting of hydroxyl, carboxyl, cyano, nitro, alkoxy, alkoxyalkyl, alkoxycarbonyl, and alkoxycarbonyl A group substituted with a group in which an oxy group is substituted. Specific examples of the alkoxy group, alkoxyalkyl group, alkoxycarbonyl group, and alkoxycarbonyloxy group which may be substituted with a naphthyl group and an alkyl-substituted naphthyl group include -39-200923579 to the aforementioned benzene. The same group as exemplified by the group in which the alkyl group and the alkyl group are substituted. In the general formula (2), preferred examples of the substituted or unsubstituted naphthyl group represented by R6 include 1-naphthyl group, 1-(4-methoxynaphthyl) group, and 1-(4-_B). Oxynaphthyl), 1-(4-11-propoxynaphthyl), 1-(4-n-butoxynaphthyl), 2-(7-methoxynaphthyl), 2-(7-ethoxynaphthyl) group, 2-(7-η-propoxynaphthyl) group, 2-(7-η-butoxynaphthyl) group, and the like. In the general formula (2), specific examples of the substituted or unsubstituted divalent group having 2 to 10 carbon atoms formed by the combination of two R6s may be formed together with the sulfur cation in the general formula (2). A 5-membered ring or a 6-membered ring (preferably a 5-membered ring (tetrahydrothiophene ring)). Further, specific examples of the substituent which may be substituted with a substituted or unsubstituted divalent group having 2 to 10 carbon atoms include those in which the phenyl group and the alkyl-substituted phenyl group are substituted. The same groups are exemplified by a trans group, a mercapto group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group or an alkoxycarbonyloxy group. R6 in the general formula (2) is a methyl group, an ethyl 'phenyl group, a 4-methoxy group, a 1-nyl group, and one R is bonded to form a divalent group of a tetrachlorophene ring structure together with a sulfur cation. The temple is better. Preferred examples of the cation moiety in the general formula (2) include a triphenylphosphonium cation, a tri-1-naphthylphosphonium cation, a tri-tert-butylphenyl cation, and a 4-fluorobenzol-one. Phenylphosphonium cation, di-4-fluorophenyl-phenylphosphonium cation, tris-fluorophenylphosphonium cation, 4-cyclohexylphenyl-diphenylphosphonium cation, 4-methanesulfonylphenyl- Diphenylphosphonium cation, 4_cyclohexa-40- 200923579 sulfonyl-diphenylphosphonium cation, 1-naphthyldimethylphosphonium diethylphosphonium cation, 1-(4-hydroxynaphthyl) Methyl 1-(4-methylnaphthyl)dimethyl sulfonium cation, 1-(4-methylethyl sulfonium cation, 1-(4-cyanonaphthyl)dimethylphosphonium cyano naphthyl) diethyl Ruthenium cation, 1-(3,5-dimethyl-4-tetrahydrothiophene cation, di(4-methoxynaphthyl)tetrahydrogen, 1-(4-ethoxynaphthyl)tetrahydrothiophene Ruthenium cation, oxynaphthyl) tetrahydrothiophene cation, 1-(4-n-butoxyhydrothiophene iron cation, 2-(7-methoxynaphthyl)tetrahydrol|sub, 2-(7-B Oxynaphthyl)tetrahydrothiophene cation, oxynaphthyl)tetrahydrothiophene iron cation, 2-( 7-n- In the general formula (3), the "CnF2n'" group is a carbon number n group. However, the perfluoroalkyl group is linear or branched. Further, 2, 4, or 8 is In the general formula (3), preferred examples of the hydrocarbon group having 1 to 12 carbon atoms substituted by R7 include an alkyl group having 12 groups, a cycloalkyl group, and a bridged alicyclic hydrocarbon group. Ethyl, η-propyl, i-propyl, η-butyl, 2-methylpropyl, t-butyl, η-pentyl, neopentyl, η-hexyl, heptyl, η-octyl a base, a 2-ethylhexyl group, a η-fluorenyl group, a η-fluorenyl-based methyl group, a hydroxy-originyl group, and an adamantyl group. In the general formulae (5) and (6), as shown by R9 Specific examples of a carbon-like or branched alkyl group containing a fluorine atom, methyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, ten ion, 1-naphthalene

Hydroxyphenyl) thiophene cation from 1-(4-η-propylnaphthyl)tetrathiophene cation from 2-(7II-propylnaphthyl)tetrafluoropropane, η is 1, substitution or No carbon number 1~ There are also methylpropyl, 1-cyclohexyl, η-, raw spinel, and female 1~10 in the boxing, which can be exemplified by trifluoropentyl, -41 - 200923579 perfluorooctyl Wait. In the general formulae (5) and (6), a specific example of a fluorine atom-containing substituted or unsubstituted divalent group having 2 to 10 carbon atoms formed by bonding two R9 groups is exemplified by tetrafluoroethylene Base, hexafluoro-propyl, octafluoro-butyl, decafluoro-pentyl, fluorene-hexyl, and the like. In the general formula (2), preferred examples of the anion site include a trifluoromethanesulfonate anion, a perfluoro-η-butanesulfonate anion, a perfluoro-η-octanesulfonate anion, and 2- (Bicyclo[2.2_1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate anion, 2-(bicyclo[2.2.1]hept-2-yl)-1,1-di A fluoroethanesulfonate anion, a 1-adamantylsulfonate anion, and an anion represented by the formula (8-1) to (8-7).

-42 - 200923579 (1), without p-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene cation, 1-(4-methoxynaphthalen-1-yl)tetrahydrothiophene Cation, 1-(4-ethoxynaphthalen-1-yl)tetrahydrothiophene cation, 1-(4-n-propoxynaphthalen-1-yl)tetrahydrothiophene cation, l-(4-n -butoxynaphthalen-1-yl) tetrahydrothiophene iron cation, 2-(7-methoxynaphthalen-2-yl)tetrahydrothiophene cation, 2-(7-ethoxynaphthalen-2-yl) Tetrahydrothiophene iron cation, 2-(7-n-propoxynaphthalenyl)tetrachloropropenyl cation, 2-(7-n-butoxynaphthalen-2-yl)tetrahydrothiophene cation a cation having a substituted or unsubstituted divalent group having 2 to 10 carbon atoms bonded thereto, and an anion of a trifluoromethanesulfonate anion, a perfluoro-?-butanesulfonate anion, a perfluoro-?- A combination of an anion represented by the general formula (3) such as an octanesulfonate anion. (Π) Other acid generator The acid generator (B) may also contain an acid other than the acid generator (1) (hereinafter also referred to as "other acid generator"). Specific examples of the other acid generator include a gun salt compound, a halogen-containing compound, a diazoketone compound, a hydrazine compound, and a sulfonic acid compound. (Iron salt compound) Specific examples of the gun salt compound include an iodine salt, a sulfonium salt, a money salt 'diazonium salt, a pyridine salt, and the like. More specifically, diphenyl iodine trigas methanesulfonate, diphenyl iodine hexafluoro-n-butane sulfonate, diphenyl iodine iron total gas _n' octane sulfonate, diphenyl iodine镊2-bicyclo[2.2.1]hept-2-yl-i'1,2,〗-tetrafluoroethanesulfonate, bis(4_t_butylphenyl) iodine triflate, bis ( 4-t-butylphenyl) iodine-n-hexafluoro-η-butanesulfonate, bis(4-butylphenyl)iodide perfluoro-heart octane sulfonate, bis(4_t_butylphenyl) ) -43- 200923579 Iodine 2_bicyclo[2_2.1]heptan-2-yl-1,1,2,2-tetrafluoroethanesulfonate, cyclohexyl-2-oxocyclohexylmethylsulfonate Fluoromethanesulfonate, dicyclohexyl 2-oxocyclohexylfluorene trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, 1-(3,5-dimethyl 4-hydroxyphenyl)tetrahydrothiophene trifluoromethanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene gun perfluoro-η-butyl sulfonate , 1-(3,5-dimethyl-4-cyclophenyl)tetrahydrothiophene perfluoro-η-octyl sulfonate, 1-(4-methoxynaphthalen-1-yl)tetrahydrothiophene Key triflate, 1-(4-methoxynaphthalen-1-yl)tetrahydrothiophene -η-butyl sulfonate, 1-(4-methoxynaphthalen-1-yl)tetrahydrothiophene gun perfluoro-η-octyl sulfonate, 1-(4-ethoxynaphthalene-buyl Tetrahydrothiophene trifluoromethanesulfonate, di(4-ethoxynaphthalen-1-yl)tetrahydrothiophene perfluoro-n-butylsulfonate, 1-(4-ethoxynaphthalene- 1-yl)tetrahydrothiophene-perfluoro-n-octylsulfonate, 1-(4-n-propoxynaphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonate, 1-(4 -n-propoxynaphthalen-1-yl)tetrahydrothiophene gun perfluoro-η-butyl sulfonate, 1-(4-n-propoxynaphthalen-1-yl)tetrahydrothiophene-perfluoro- Η-octyl sulfonate, 1-(4-η-butoxynaphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonate, b (4-n-butoxynaphthalen-1-yl) Tetrahydrothiophene fluorene perfluoro-η-butyl sulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene iron perfluoro-η-octyl sulfonate, 2- (7) -Methoxynaphthalen-2-yl)tetrahydrothiophene trifluoromethanesulfonate, 2-(7-methoxynaphthalen-2-yl)tetrahydrothiophene-perfluoro-η-butylsulfonate, 2-(7-Methoxynaphthalen-2-yl)tetrahydrothiophene-perfluoro-η-octylsulfonate, 2-(7-ethoxynaphthalen-2-yl)tetrahydrothiophene trifluoromethyl Sulfonate, 2- (7-ethoxynaphthalen-2-yl)tetrahydrothiophene gun perfluoro-η-butyl sulfonate, 2_(7-ethoxynaphthalene-2-yl)tetrahydrothiophene gun perfluoro-η-octane Sulfonate, -44- 200923579 2-(7-n-propoxynaphthalen-2-yl)tetrahydrothiophene trifluoromethanesulfonic acid (7-n-propoxynaphthalen-2-yl)tetrahydrogen Thiophene-perfluoro-η-butylsulfo-2-(7-n-propoxynaphthalen-2-yl)tetrahydrothiophene gun perfluoro-η-octane salt, 2-(7-n-butoxynaphthalene- 2-yl) tetrahydrothiophene trifluoromethyl 2-(7-n-butoxynaphthalen-2-yl)tetrahydrothiophene gun perfluoro-η-butyl salt, 2-( 7-n-butoxy Naphthyl-2-yl)tetrahydrothiophene iron perfluoro-η-acid salt, and the like. (Heterane-containing compound) Specific examples of the halogen-containing compound include a hydrocarbon compound and a halogenated alkyl group-containing heterocyclic compound. More phenylbis(trichloromethyl)-s-triazine, 4-methoxyphenylbis(yl)-s-triazine, 1-naphthylbis(trichloromethyl)-s-three (S)-(s)-triazine derivatives; 1,1-bis(4-chlorophenyl).2,2,2-three. (Azidone compound) Specific examples of the azide compound include a 1,3-diazide compound, an azide p-benzoquinone compound, and an azide naphthoquinone compound, and specific examples thereof include 1,2-naphthoquinone. Azide-4-sulfonyl chloride, 1,2-azido-5-sulfonyl chloride, 2,3,4,4'-tetrahydroxybenzophenone quinonediazide-4-sulfonate Acid ester or 1,2-naphthoquinonediazide-5-sulfonate, 1,2-naphthoquinonediazide-4-sulfonate or quinonediazide of 1 (4-hydroxyphenyl)ethane -5-sulfonate and the like. (飒 compound) Specific examples of the ruthenium compound include β oxo oxime, a salt ' 2 - acid salt, a sulfonate, and a sulfonic acid octyl sulfonate. The base may be trichlorotrichlorochlorochloride. B hospital oxygen -2- and so on. More naphthoquinone di 1,2-naphthalene, 1, phenylidene 1,2-naphthalene β-sulfonium -45- 200923579 飒, or α-azido compound of these compounds, and the like. More specifically, 4-nonacetophenone maple, mesitylene acetophenone oxime, bis(phenylsulfonyl)methane, and the like can be given. (sulfonic acid compound) Specific examples of the sulfonic acid compound include an alkylsulfonate, an alkylsulfonimide, a haloalkylsulfonate, an arylsulfonate, and an imidesulfonate. More specifically, benzoin benzene sulfonate, pyrogallol (trifluoromethanesulfonate), nitrobenzyl-9,10-diethoxyindole-2-sulfonate, Trifluoromethanesulfonylbicyclo[2.2.1]heptane-5-ene-2,3-dicarbodiimide, nonafluoro-n-butylsulfonylbicyclo[2.2.1]heptane-5-ene -2,3-dicarbodiimide, perfluoro-η-octylsulfonylbicyclo[2.2.1]heptane-5-ene-2,3-dicarbodiimide, 2-bicyclo[2.2_1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonylbicyclo[2.2.1]heptane-5-ene-2,3-dicarbodiimide, fluorene-(trifluoromethanesulfonate醯oxy)butanediamine, fluorene-(nonafluoro-η-butylsulfonyloxy)butaneimine, fluorene-(perfluoro-η-octanesulfonyloxy)butanediimide ,Ν-(2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy)butaneimine, 1,8-naphthalenedicarboxylic acid imine Trifluoromethanesulfonate, 1,8-naphthalene dicarboxylic acid imine, nonafluoro-η-butanesulfonate, 1,8-naphthalene dicarboxylic acid imine, perfluoro-η-octanesulfonate, and the like. Among the above other acid generators, diphenyl iodide trifluoromethanesulfonate, diphenyliodonium nonafluoro-η-butanesulfonate, diphenyliodopyl perfluoro-η-octanesulfonic acid Salt, diphenyl iodide iron 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis(4-t-butylphenyl) iodine gun three Fluoromethanesulfonate, bis(4-t-butylphenyl)iodo-iron nonafluoro-η-butanesulfonate, bis(4-t-butylbenzene-46 - 200923579 base) iodine-perfluoro-n -octanesulfonate, bis(4-t-butylphenyl)iodonium 2_bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, cyclohexyl .2-oxocyclohexyl.methylfluorene trifluoromethanesulfonate, dicyclohexyl 2-oxocyclohexylfluorene trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate Acid salt, trifluoromethanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide, nonafluoro-n-butylsulfonylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarbodiimide, perfluoro-η-octylsulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide, 2-bicyclo[2.2.1 ]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide , Ν-(trifluoromethanesulfonyloxy)butaneimine, fluorene-(nonafluoro-η-butylsulfonyloxy)butaneimine, fluorene-(perfluoro-η-octanesulfonate) Oxy)butane diimine, Ν-(2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy)butanediimide, 1, 8-Naphthalene dicarboxylic acid imine trifluoromethanesulfonate is preferred. Further, the other acid generators may be used singly or in combination of two or more. (2) The content ratio of the acid generator (Β) contained in the linear composition of the radiation sensitive agent of the present invention ensures the quality of the polymer (Α) 100 as a viewpoint of sensitivity and development of the photoresist. The portion is generally from 0. 1 to 20 parts by mass, preferably from 〇5 to 10 parts by mass. If the content ratio is less than ο·1, the sensitivity and developability tend to decrease. On the other hand, when 20 parts by mass is known, the transparency to radiation is lowered. It is difficult to obtain a rectangular photoresist pattern. Further, the content ratio of the other acid generator is encapsulated in the acid generator (Β) 1 〇 〇 by mass%, and is generally 80 衅. Below /°, the alumina is 60% by mass or less. Further, the lower limit of the content ratio of the other acid generator is not particularly limited to -47 to 200923579, and may be 5% by mass or more as necessary. 3 Nitrogen-containing compound The radiation-sensitive linear composition of the present invention may optionally contain a nitrogen-containing compound (C). The nitrogen-containing compound (C) is a component which controls the diffusion phenomenon in the photoresist film of the acid generated by the acid generator (B) by exposure, and suppresses the poor chemical reaction in the non-exposed region. By containing the nitrogen-containing compound (C), the storage stability of the obtained linear radiation sensitive composition can be improved, the resolution as a photoresist can be further improved, and the pulling time from the exposure to the post-exposure heat treatment can be suppressed. The linear amplitude change of the photoresist pattern caused by the change of (PED) can obtain a linear composition of sensitive radiation with excellent process stability. Further, the nitrogen-containing compound (C) may contain only one nitrogen-containing compound (C)' but may contain two or more kinds of nitrogen-containing compounds (C). (1) Component The nitrogen-containing compound (C) is preferably a nitrogen-containing compound represented by the general formula (9) (hereinafter also referred to as "nitrogen-containing compound (1)").

In the general formula (9), Rl5 and R16 independently of each other represent a hydrogen atom, a substituted or unsubstituted, linear, branched or cyclic group having a carbon number of 1 to 2 0-48-200923579, an aryl group, Or aralkyl. Further, in the general formula (9), R15 or R16 are bonded to each other, and together with each bonded carbon atom or nitrogen atom, a divalent saturated or unsaturated hydrocarbon group having a carbon number of 4 to 20 or a derivative thereof is formed. (i) Nitrogen-containing compound (1) Specific examples of the nitrogen-containing compound (1) include Nt-butoxy-based----!--N-amine, Nt-butoxy-based _- !--nonylamine, Nt-butoxycarbonyldi-η-decylamine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl -2-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, (S)-(-)-1-(t-butoxycarbonyl)-2-pyrrole Alkanol, (R)-(+)-1-(t-butoxycarbonyl)-2-pyrrolidinemethanol, Nt-butoxycarbonyl-4-hydroxypiperidine, Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbonylpiperazine, N,N-di-t-butoxycarbonyl-bumantylamine, N,N-di-t-butoxycarbonyl-N-methyl-1-adamantane Amine, Nt-butoxycarbonyl-4,4'-diaminediphenylmethane, anthracene, Ν'-di-t-butoxycarbonylhexamethylamine, N,N,N',N '-Tetra-t-butoxycarbonylhexamethyldiamine, N,N'-di-t-butoxycarbonyl-1,7-diamine heptane, hydrazine, Ν'-di-t-butyl Oxycarbonyl-1,8-diamine octane, anthracene, Ν'-di-t-butoxycarbonyl-1,9-diamine Decane, hydrazine, Ν'-di-t-butoxycarbonyl-1,10-diamine decane, hydrazine, Ν'-di-t-butoxycarbonyl-1,12-diaminedodecane, N,N,B-t-butoxy ore - 4,4'--amine _•Phenyl, Nt-butoxy-based benzimidazole, Nt-butoxycarbonyl-2-methyl The Nt-butoxycarbonyl group such as benzimidazole or Nt-butoxycarbonyl-2-phenylbenzimidazole contains an amine compound. (i i ) Other nitrogen-containing compound Further, the nitrogen-containing compound (C) may be a nitrogen-containing compound other than the nitrogen-containing compound (1) - 49-200923579 (hereinafter also referred to as "other nitrogen-containing compound"). Specific examples of the other nitrogen-containing compound include a tertiary amine compound, a fourth-order ammonium hydroxide compound, and other nitrogen-containing heterocyclic compounds. (Grade 3 amine compound) Specific examples of the tertiary amine compound include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, and tri- Tri(cyclo)alkylamines such as η-heptylamine, tri-η-octylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, and tricyclohexylamine. (4th-order ammonium hydroxide compound) Specific examples of the 4-stage ammonium hydroxide compound include tetra-n-propylammonium hydroxide and tetra-n-butylammonium hydroxide. (Nitrogen-containing heterocyclic compound) Specific examples of the nitrogen-containing heterocyclic compound include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4·ethylpyridine, and 2-phenyl. Acridinium, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, niacinamide, quinoline, 4-hydroxyquinoline, 8-hydroxyquinoline, acridine, etc. Pyridines; piperazines, piperazines such as 1-(2-hydroxyethyl)piperazine; pyrazine, pyrazole, pyridazine, Quinozaline, hydrazine, pyrrolidine, piperidine, 3-hexahydropyridine-hydrazine, 2 -propanediol, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, imidazole, 4-methylimidazole, 1 -benzylmethyl-2-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl -2-Methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole, and the like. In addition to the above other nitrogen-containing compounds, aniline, N-methyl-50-200923579 aniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, An aromatic amine such as 4-nitroaniline, 2,6-dimethylaniline or 2,6-isopropylaniline; an alkanolamine such as triethanolamine or N,N-di(hydroxyethyl)aniline; N,N,N',N'-tetramethylethylidene diamine, N,N,N',N'-indole (2-hydroxypropyl)-ethylidene diamine, 1,3-double (4-Aminophenyl)-1-methylethyl]benzenetetramethylamine, bis(2-dimethylaminoethyl) oxime, bis(2-diethylaminoethyl) Ether, etc. (2) Content ratio The content ratio of the gas-containing compound (C) contained in the linear composition for radiation of the present invention is 100 parts by mass for the viewpoint of ensuring higher sensitivity as a photoresist. The phrase 'generally is less than 1 part by mass, preferably less than 5 parts by mass. When the content ratio exceeds 1 part by mass, the sensitivity as a photoresist tends to be remarkably lowered. When the content ratio of the nitrogen-containing compound (C) is less than 0.001 part by mass, the pattern shape or the dimensional fidelity may be lowered by the process conditions. 4 Additive (D) The radiation sensitive linear composition of the present invention may contain various additives (D) as necessary. Specific examples of the additive (D) include a fluorine-containing resin additive (d 1 ), an alicyclic skeleton-containing additive (d 2 ), a surfactant (d3), and a sensitizer (d4). The content ratio of these additives (D) can be appropriately set in accordance with the nature of the additives (D) or the purpose of use. (Fluorine Resin Additive (d 1 )) The fluorine-containing resin additive (d丨) is particularly a component which exhibits the function of water repellency on the surface of the film in the immersion exposure of the photoresist - 51 - 200923579. Further, the fluorine-containing resin additive (d 1 ) can suppress the elution of the components from the photoresist film to the liquid immersion exposure liquid, and even if the liquid immersion exposure is performed by high-speed scanning, no droplets remain, and the display can be effectively suppressed. A component of the effect of a defect in liquid immersion exposure such as a watermark defect. Further, the structure of the fluorine-containing resin additive (d 1 ) is not particularly limited, but it is preferable to have the characteristics of (dl-Ι) to (dl-4) shown below. (dl-Ι): This is a fluorine-containing resin additive which is insoluble in the developing solution and is soluble in alkali by acid action. (d 1 - 2 ): The fluorine-containing resin additive which is soluble in the developing solution and which increases the solubility of the alkali by the action of an acid. (d 1 - 3 ): the fluorine-containing resin additive which becomes insoluble in the developing liquid by the action of alkali. (d 1 - 4 ): The fluorine-containing resin additive which is soluble in the developing solution and which increases the solubility of alkali by the action of alkali. The fluorine-containing resin additive (d1) having any of the above characteristics (dl-1) to (dl-4) is a resin containing at least one of the above-mentioned repeating unit (6) and the following fluorine-containing repeating unit. Or more than at least one selected from the group consisting of repeating units (1) to (5), (7), and

The resin or the like of the repeating unit in which the complex unit is a group D. The fluorine-containing repeating unit can be obtained, for example, by polymerizing a specific fluorine-containing monomer. Specific examples of the polymerization of the specific fluorine-containing monomer include trifluoromethyl (meth)propionic acid ester, 2,2,2-trifluoroethyl (meth)acrylate, and perfluoroethyl ( Methyl) acrylate, perfluoro n-propyl (meth) acrylate, perfluoro-1-propyl (meth) acrylate, perfluoro η butyl butyl-52- 200923579 (meth) acrylate, perfluoro I-butyl (meth) acrylate, perfluoro t-butyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2-(1,1,1,3,3,3- Hexafluoro)propyl (meth) acrylate, 1-(2,233,4,4,5,5-octafluoro)pentyl (meth) acrylate, 1-(2,2,3,3,4, 4,5,5-octafluoro)hexyl (meth) acrylate, perfluorocyclohexylmethyl (meth) acrylate, 1-(2,2,3,3,3-pentafluoro)propyl (A) Acrylate, 1-(2,2,3,3,4,4,4-heptafluoro)pentyl (meth) acrylate, 1- (3,3,4,4,5,5,6 ,6,7,7,8,8,9,9,10,10,10-heptadecafluoro)fluorenyl (meth) acrylate, 1-(5-trifluoromethyl-3,3,4, 4,5,6,6,6-octafluoro)hexyl (meth) acrylate, and the like. As the fluorine-containing resin additive (d 1 ), a polymer represented by the general formula (1 0-1) to (10-7) is preferred. Further, in the general formulae (10-1) to (10-7), R1 represents a hydrogen atom, a methyl group or a trifluoromethyl group. -53 200923579 【化1 8】

(10-7) -54- 200923579 (additive (d2) containing an alicyclic skeleton) The additive (d2) containing an alicyclic skeleton is intended to further improve dry etching resistance, pattern shape, adhesion to a substrate, and the like. The ingredients of the role. Specific examples of the additive (d2) containing the alicyclic skeleton include 1-adamantanecarboxylic acid, 2-adamantanone, 1-adamantanecarboxylic acid t-butyl ester, and 1-adamantanecarboxylic acid t-. Butoxycarbonylmethyl ester, h-adamantanecarboxylic acid α-butyrolactone, I,3-adamantane dicarboxylic acid di-t-butyl ester, 1-adamantane acetic acid t-butyl ester, 1-adamantanic acid t -Adamoxycarbonylmethyl ester, iota, adamantane diacetate di-t-butyl ester, 2,5-dimethyl-2,5-di(adamantylcarbonyloxy)hexane, adamantane derivative Species; t-butyl deoxycholate, t-butoxycarbonyl methyl deoxycholate, 2-ethoxyethyl deoxycholate, 2-cyclohexyloxyethyl deoxycholate, deoxycholic acid 3 Deoxycholate such as oxocyclohexyl ester, tetrahydropyranyl deoxycholate, and mevalonol deoxycholate; t-butyl lithic acid, t-butoxycarbonyl group of lithocholic acid Ester, 2-ethoxyethyl lithate, 2-cyclohexyloxyethyl lithate, 3-oxocyclohexyl lithate, tetrahydropyranyl lithochate, thiocyanate Cholinate such as lactone lactone; dimethyl adipate, diethyl adipate, dipropyl adipate, adipate η -Alkyl carboxylates such as butyl ester and di-t-butyl adipate; 4-[2-hydroxy-2,2-bis(trifluoromethyl)ethyl]tetracyclo[6.2_1.13, 6.02' 7] Dodecane, 2-hydroxy-9-methoxycarbonyl-5-oxo-4-oxo-tricyclo[4.2.1.〇3'7]decane, and the like. Further, the additives (d 2 ) containing the alicyclic skeleton may be used singly or in combination of two or more. (Brier Active Agent (d3)) -55-200923579 The surfactant (d3) is a component which exhibits an effect of improving coatability, a strip, and the like. As such a surfactant (d3), polyethylene oxide lauryl ether, polyethylene oxide stearyl ethane oleyl ether, polyethylene oxide η-octyl phenyl ether, polyepoxy Z phenyl ether Others, polyethylene glycol dilaurate, polyethylene glycol distearyl surfactant, the following trade names, manufactured by Vietnam Chemical Industry Co., Ltd., Polyflow No. 75, and No. Co., Ltd. Company system), F-TopEF301, and EF352 (above, TOHKEM PRODUCTS company FF 1 7 1, same as F 1 7 3 (above, Dainippon Ink: system), Flora FC430, with FC431 (above, Living system), AsahiGuard AG71 0, SurflonS-3 8 2. Same as SC-102, same as SC-1 03, same as SC-104, same as SC-1 05, (above, Asahi Glass Co., Ltd.), etc. The activity may be used singly or in combination of two or more kinds. (sensitizer (d4)) The sensitizer (d4) is a sensitizing agent (B) which absorbs radiation energy, thereby showing an increase in the amount of acid generated. Specific examples of the sensitizer (d4) showing the effect of improving the sensitivity of the linear composition of the sensitive radiation include azoles and benzophenones. Classes, naphthalenes, phenols, diacetyl groups, eosin, mons, terpenoids, phenothiazines, etc., and their sensitizers (d4 alone or in combination of two or more. Also, sensitive radiation The linear composition may contain a dye or a pigment pattern, a specific example of development, an ether, a polyepoxydialkyl η-mercaptoate, etc. (Non-Frequency 1-5 (above, EF303, same), Megefology) Industrial company friend 3Μ company SC-101, the same SC -1 0 6 agent (d3) energy is transmitted to the player, and can be expressed as a single such as acetamidine, digalaine, ruthenium. Containing dyes - 56- 200923579 $II material time can visualize the latent image of the exposure part, and mitigate the influence of halation during exposure. Further, when the adhesion aid is contained, the adhesion to the substrate can be improved. The additive (D) may, for example, be a gastric-soluble resin, a low-molecular alkali solubility control agent having an acid-dissociable protecting group, a halation preventing agent, a storage stabilizer, an antifoaming agent, etc. D) may be used alone or in combination of two or more. 5 Solvent (E) The sensitive linear composition of the radiation may contain various solvents (E) as necessary. The solvent (E) is not particularly limited as long as it can dissolve the polymer (A) and the acid generator (B). The nitrogen-containing compound (C) and the additive (D) may be dissolved. Specific examples of the solvent (E) include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol mono- Η-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-η-butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate Propylene glycol monoalkyl ether acetate such as ester, propylene glycol mono-t-butyl ether acetate; cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-di a cyclic ketone such as methylcyclohexanone or isophorone; 2_butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanyl a linear or branched ketone such as 3-methyl-2-pentamethylene, 3,3-dimethyl-2-butanone, 2-heptanone or 2-octanone; 2-hydroxypropionic acid Ester, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate, 2-hydroxypropane Acid i-propyl ester, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate, t-butyl 2-hydroxypropionate, etc. Acid alkyl ester-57 - 200923579; 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxy oxy acid methyl ester, 3-ethoxypropionic acid ethyl ester, etc. The alkyl oxypropionates may also be η-propanol, i-propanol, n-butanol, t-butanol, cyclohexanol, ethyl monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol. Mono-η-propyl ether, ethylene glycol butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene η-propyl ether, diethylene glycol di-η-butyl ether, ethylene glycol Monomethyl ether acetate glycol monoethyl ether acetate, ethylene glycol mono-η-propyl ether acetate, dimethyl dimethyl ether, propylene glycol monoethyl ether, propylene glycol mono-η-propyl ether, toluene, benzene, 2-hydroxyl Ethyl 2-methylpropionate, ethyl ethoxyacetate, ethyl acetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutylacetate 3-methyl_3_A Oxybutyl acetate, 3-methyl-3-methoxybutyl ester, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, acetate, η-butyl acetate Ester, B Methyl acetate, ethyl acetate, ethyl acetate, methyl ester, ethyl pyruvate, hydrazine-methylpyrrolidone, ν, Ν-dimethylamine, hydrazine, hydrazine-dimethylacetamide, benzyl ether, Di-n-hexyl ether, monool monomethyl ether, monoethyl alcohol monoacetic acid, hexanoic acid, octanoic acid, ι_辛 sterol, benzyl alcohol, benzyl acetate, ethyl benzoate, oxalate, Malay Diethyl acid, γ-butyrolactone, ethylene carbonate, propylene carbonate, and the like. Among them, propylene glycol monoalkyl ether acetate is preferred, and a solvent containing propylene monomethyl acetate is more preferred. Further, a cyclic ketone, a ketone-like ketone, a 2-hydroxypropionic acid alkyl ester, a 3-alkoxypropionic acid or γ-butyrolactone is also preferable. Moreover, the solvent (Ε) may be a mono-propyl group, a mono-, a diol mono-η-alcohol di-, an ethanol mono-dimethyl ethyl ester, a propionic acid η-propanone, a brewing diethylene, a 1-jene Ester esters or alkane cool or -58- 200923579 Combination of more than two kinds of use. Method of Forming II Photoresist Pattern The sensitive radiation linear composition of the present invention can be used as a chemically amplified type of photoresist. The chemically amplified photoresist is obtained by dissociating the acid dissociable group in the polymer (A) into a carboxyl group by the action of an acid generated by the acid generator, thereby improving the dissolution of the alkaline developing solution by the photoresist exposed portion. As a result, the exposed portion was dissolved and removed by an alkaline developing solution to obtain a positive resist pattern (hereinafter also referred to simply as "resist pattern type"). The photoresist pattern is formed by (1) forming a photoresist film on a substrate using a linear composition of a sensitive radiation (hereinafter also referred to as "step (1)"), and (2) forming a photoresist film. It is necessary to pass the liquid immersion exposure liquid through a mask having a predetermined pattern and expose it by radiation (hereinafter also referred to as "step (2)"), and (3) to develop an exposed photoresist film. The step of forming a photoresist pattern (hereinafter also referred to as "step (3)"). When immersion exposure is performed, if it is necessary to directly contact the liquid immersion exposure liquid to protect the photoresist film, firstly, in step (2), the insoluble liquid is immersed in the liquid immersion exposure liquid to form a protective film on the photoresist film. It is better. The protective film for liquid immersion has a solvent-peelable liquid immersion protective film which can be peeled off in a solvent in the step (3) (for example, refer to JP-A-2000-06292) and the steps. (3) A developing solution for liquid-dissolution type liquid immersion which can be peeled off while developing a medium image (for example, refer to International Publication No. 2 0 0 5 / 〇6 9 0 6 6 and International Publication No. 2 00 5 /0 3 5 790 manual), etc., but there is no special limit. However, it is preferable to use a protective liquid film of the latter liquid-dissolution type liquid immersion -59-200923579 from the viewpoint of the amount of conveyance. 1 Step (1) Step (1) is a composition solution obtained by linearly treating the sensitive radiation of the present invention with a solvent, by a suitable coating means such as spin coating or cast coating, for example, a silicon wafer, A step of forming a photoresist film on a substrate such as a dioxide wafer. Further, the coating solution is applied until the formed photoresist film becomes a predetermined film thickness pre-baked (PB). The thickness of the photo-resist film is not particularly limited, and is generally 01 to preferably 0 . 1~2 μ m. Further, the heating condition of the prebaking can be appropriately set depending on the composition of the composition, and is usually 200 ° C, preferably 50 to 150 ° C. Further, it is preferable to form an organic or inorganic film on the substrate, as disclosed in Japanese Patent Laid-Open Publication No. Hei. No. Hei. Further, it is desirable to prevent a basic film from being contained in the environmental gas. For example, a protective film can be provided on the film disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. Further, the liquid may be immersed in a protective film. These technologies can be used. 2 Step (2) Step (2) is that the photoresist film formed in the step (1) is subjected to a liquid immersion exposure liquid such as water, and is exposed through a light having a predetermined pattern of light. The radiation to be irradiated is specifically characterized by visible light rays, ultraviolet rays, far ultraviolet rays, X-rays, a solution-dissolving coating, and roll coating, and then a resist film. 5 μ m, sensitive light ray is 30~ stretched to the maximum 59-93448. The reflection is anti-impurity, and the photoresist is formed on the photoresist. It is necessary to cover and put the type, and the electric particle beam can be -60-200923579. However, it is suitably selected in accordance with the kind of the acid generator (B) contained in the linear composition of the sensitive radiation. However, it is preferable to irradiate a far ultraviolet line mainly composed of an ArF excimer laser (wavelength I93 nm) or a KrF excimer laser (wavelength 24 8 nm), and it is more preferable to irradiate an ArF excimer laser. Further, the exposure conditions such as the amount of exposure can be appropriately selected in accordance with the composition of the linear composition of the radiation sensitive agent or the type of the additive. And it is preferred to carry out heat treatment (PEB) after exposure. By carrying out PEB, the dissociation reaction of the acid dissociable group in the polymer (A) can be smoothly carried out. The heating condition of P EB can be appropriately selected by the composition of the linear composition of the sensitive radiation, etc., and is generally 30 to 200 ° C, preferably 50 to 170 ° C. 3 Step (3) Step (3) is a step of forming a predetermined photoresist pattern by developing the exposed photoresist film. Examples of the developing liquid used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, gas, ethylamine, η-propylamine, diethylamine, and di-n. _ propylamine, triethylamine, methyl;:: ethylamine, ethyl dimethylamine, triethanolamine, tetramethyl hydroxy hydroxide, shame, piperidine, choline, guanidine, 8-diazabicyclo- Preferably, at least / a dissolved alkaline aqueous solution of a basic compound such as carbon dilute, 1,5-diazabicyclo-[4.3_0]-5-decene is preferred. The concentration ' of the alkaline aqueous solution' is usually 1% by mass or less. When the concentration of the alkaline aqueous solution exceeds 10% by mass, the possibility that the non-exposed portion is also dissolved in the developing liquid is increased. Further, an organic solvent may be added to the developing solution (alkaline aqueous solution). Examples of the organic solvent to be added include acetone, methyl ethyl ketone, methyl 1-butanone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethyl ring. Ketones such as ketones; methanol, ethanol, η-propanol, i-propanol, η-butanol, 1-butanol, cyclopentanol, cyclohexanol, 1,4-hexanediol And alcohols such as 1,4 -hexanedimethylol; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate, n-butyl acetate and i-amyl acetate; aromatics such as toluene and xylene Hydrocarbons, or phenols, acetone acetone, dimethylformamide, and the like. Further, the organic solvents may be used singly or in combination of two or more. The amount of the organic solvent to be added is preferably 1 part by volume or less based on 1 part by volume of the aqueous alkaline solution. When the amount of the organic solvent added exceeds 100 parts by volume based on 1 part by volume of the aqueous alkaline solution, the development property is lowered, and the image retention of the exposed portion tends to increase. Further, it is preferred to add an appropriate amount of a surfactant or the like to the developing solution (basic aqueous solution). After development using a developing solution (alkaline aqueous solution), it is usually washed with water and allowed to dry. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to these Examples. In addition, in the examples and comparative examples, "parts" and "%" are based on mass unless otherwise specified. Further, the measurement methods of various physical properties and the evaluation methods of the respective characteristics are as follows. [Mw and Μη]: GPC column manufactured by Tosoh Co., Ltd. (two product names "G2000HXL", one product name "G3 000HXL", one product name "G4000HXL") flow rate: 1.0 mL/min, dissolution Solvent: tetrahydrofuran, column temperature: 4 (Measured under TC conditions, by gel permeation chromatography (GPC) using mono-62-200923579 dispersed polystyrene as a standard. Further, dispersion (Mw/Mn) It is calculated from the measurement results of Mw and Μη. [13C-NMR analysis]: The product name "JNM-EX270" manufactured by Sakamoto Electronics Co., Ltd. was used to perform "C-NMR analysis of each polymer." Content ratio of low molecular weight component]: The product name "Intersil ODS-25pm column" (4.6 mm < j) x 25 0 mm) manufactured by GL Sciences, flow rate: 1.0 mL / min, solvent: acrylonitrile / 0.1 The measurement was carried out by high-speed liquid chromatography (HPLC) under the analysis conditions of a % phosphoric acid aqueous solution. (Synthesis Example 1) 42.04 g (40 mol%) of monomer (M1), 42.26 g (45 mol%) of monomer (M-2), and 15_70 g (15 mol%) of monomer (M-3) were dissolved in 200 g of 2 Butanone, a monomer solution obtained by adding 4.61 g of dimethylazobisisobutyrate was placed in a dropping funnel. A 500 mL three-necked flask containing l〇〇g of 2-butanone was placed in a nitrogen purge for 30 minutes, and then stirred under stirring with 2-butanone to 80 X: 'The monomer solution from the dropping funnel was UmL/min. The speed was dripped' to start the reaction for 6 hours from the start of the drip. After the completion of the reaction, the reaction solution which was cooled to 30 ° C or lower by cold water was put into 1500 g of n-heptane to precipitate a white powder. The precipitated white powder was filtered, and washed twice with a slurry of 300 g of η-heptane. After filtration, drying was carried out under vacuum at 70 ° C for 7 hours to give 79.2 g of a white powdery polymer (A-1). And the yield was 79%. -63- 200923579 The obtained polymer (A·1 ) had an Mw of 73 20 and a Mw/Mn of 1.71. Further, as a result of 13C-NMR analysis, the content ratio of the repeating unit derived from the monomer (M-1), the repeating unit derived from the monomer (M-2), and the repeating unit derived from the monomer (M-3) was 40.8. /44.l/15.1 (m〇1 ratio). Further, the content ratio of the low molecular weight component derived from the monomer was 0.03%. Further, the structural formulas of the monomers (M-1) to (M-9) are as follows. 【化20】

(M-1) (M-2) (M-3) (M-4) (M-5) (M-6)

(Synthesis Examples 2 to 7) Polymers (A - 2 ) to (a _ 7 ) were obtained in the same manner as in the above Synthesis Example 1 except for the formulations shown in Table 1. The results of various analyses are shown in Table 2 -64- 200923579 [Table 1] No. Polymer (8) Monomer 1 Monomer 2 Monomer 3 Initiator Purification solvent yield (%) Species (mol%) Species m. Lithium (mol%) Species (mol%) Species (mol%) 12 Synthesis Example 1 Α-1 Μ-1 40 M-2 45 M-3 15 MAIB11 5 η-n-heptane 79 Synthesis Example 2 Α-2 Μ-1 50 M-4 40 M-5 10 MAIB11 5 Methanol 78 Synthesis Example 3 Α-3 Μ-6 40 M-2 45 M-3 15 MAIB11 5 η-n-heptane 75 Synthesis Example 4 Α-4 Μ-6 50 M-4 40 M-5 10 MAIB11 5 Methanol 76 Synthesis Example 5 Α- 5 Μ-1 40 M-7 45 M-3 15 MAIB11 5 η-n-heptane 79 Synthesis Example 6 Α-6 Μ-1 40 M-8 45 M-3 15 MAIB11 5 η-n-heptane 78 Synthesis Example 7 Α-7 Μ-1 40 M-2 45 M-9 15 MAIBn 5 η-n-heptane 79 Μ: dimethylazobisisobutyrate* 2 : ratio of the total of monomers 1 to 3 [Table 2]

Mw Mw/Mn Low molecular weight component (% by mass) 13C analysis result (mol%)" Monomer 1 Monomer 2 Monomer 3 Synthesis Example 1 7320 1.71 0.03 40.8 44.1 15.1 Synthesis Example 2 7420 1.63 0.06 50.6 39.2 10.2 Synthesis Example 3 7290 1.69 0.04 41.2 44.0 14.8 Synthesis Example 4 7380 1.62 0.05 51.1 39.0 9.9 Synthesis Example 5 7365 1.63 0.03 40.0 44.3 15.7 Synthesis Example 6 7370 1.65 0.03 40.7 44.5 14.8 Synthesis Example 7 7375 1.64 0.04 39.8 44.1 16.1 1 1 '·From each monomer Content ratio of repeating unit -65-200923579 (Example 1) After mixing each component according to the prescription shown in Table 3, the linear composition of the radiation radiation was prepared, and the components other than the polymer (A) are as follows. The linear composition of the modulated sensitizing radiation was evaluated according to the method shown below. The evaluation results are shown in Table 4. [Table 3] Polymer (4) Acid generator (B) Nitrogen-containing compound (C) Solvent (6) PB PEB Type of mass parts Types of mass parts Types Parts by mass Parts Temperature time Temperature time (°C) (minutes) (°C) (minutes) Example A-1 50 B-1 2 C-1 0.23 E-1 1400 110 60 115 60 1 A-2 50 B-2 2 E-2 600 Example A-5 100 B-1 2 CI 0.23 E-1 1400 110 60 90 60 2 B-2 2 E-2 600 Example A-6 100 B-1 2 C-1 0.23 E-1 1400 110 60 120 60 3 B-2 2 E-2 600 Example A-7 100 B-1 2 C-1 0.23 E-1 1400 110 60 115 60 4 B-2 2 E-2 600 Comparative Example A-3 50 B- 1 2 C-1 0.23 E-1 1400 110 60 115 60 1 A-4 50 B-2 2 E-2 600 <acid generator (B ) > (B-1 ) : 4-cyclohexylphenyl Phenylhydrazine·nonafluoro-η-butanesulfonate (Β-2): triphenylsulfonium·1,1,2,2-tetrafluoro-2-(prostanbulin-2-yl)ethanesulfonate <Nitrogen-containing compound (C) > (C-1) · Nt-butoxycarbonyl D ratio (solvent (E) > (E-1): propylene glycol monomethyl ether acetate - 66 - 200923579 (E - 2 ): Ethyl lactate (sensitivity (unit: mj/cm2)]: using a coating agent/developer (C 〇at 〇r/D eve 1 op er ) (trade name "CLEAN TRACK ACT8" "Available from Tokyo Electron Co., Ltd." as a substrate, a bottom antireflection film (trade name "ARC29A", manufactured by Blois Scientific Co., Ltd.) having a thickness of 77 nm was formed on the surface of a 12-inch sand wafer. Thereafter, the linear composition of the radiation radiation was spin-coated on the above substrate by a coating agent/developer (Coator/Developer), and baked (PB) under the conditions shown in Table 3 to form a film thickness of 120 nm. Photoresist film. Next, an ArF excimer laser exposure apparatus (trade name "NSR S306C", Nicon Corporation, lighting conditions; NAO.78 Sigma 0.93/0.69) was used, and the photoresist film was exposed through a mask pattern. Thereafter, after baking (PEB) under the conditions shown in Table 3, it was developed by a 2.38 % tetramethylammonium hydroxide aqueous solution '30 ° C for 30 seconds, washed with water and dried to form a positive Type of photoresist pattern. For the obtained photoresist film, an exposure amount (mJ/cm2) when a line having a line width of 90 nm and a line-to-line distance of 90 nm (line and space is a pair of 1) is formed. As the optimum amount of exposure. The optimum exposure amount was evaluated as the sensitivity. Further, the measurement of the distance between the line and the line and the line was carried out using a scanning electron microscope (trade name "S-9380", manufactured by Hitachi High-Technologies Corporation). [Resolution (unit: nm)]: In the line width of the line and space pattern of the sensitivity and the line and space, the minimum line width (nm) of the line was evaluated as the resolution. Moreover, the smaller the resolution, the better the smaller the number of resolutions. -67 - 200923579 [The cross-sectional shape of the pattern]: The 90 nm line and the line and space pattern of the photoresist film obtained by the evaluation of the sensitivity are scanned electron microscopes manufactured by Hi-Tech Co., Ltd. The name "S-4 8 00") was observed, and the line width Lb in the middle of the photoresist pattern and the line width La on the upper portion of the film were measured. The measurement result was evaluated as "good" when the enthalpy calculated by (La-Lb) / Lb was within the range of 0 · 9 $ (La-Lb) / LbSl.l, and "bad" when the range was outside. [LWR (unit: nm)]: In the observation of the 90 nm line and space pattern of the resolution in the optimum exposure amount of the sensitivity, the evaluation of the sensitivity is the same as that of the scanning electron microscope. When the upper part of the pattern was observed, the line width was observed at an arbitrary point, and the deviation of the measurement was evaluated at 3σ (nm). [Minimum pre-destruction size (unit: nm)]: 90nm line and space in the optimum exposure amount for sensitivity evaluation. In the observation of the pattern type, the exposure is larger than the optimum exposure amount. When the exposure is performed under the amount, the obtained pattern has a finer line width, so that the photoresist pattern is finally deteriorated. The line width in the maximum exposure amount which is not confirmed to be corrupted by the photoresist pattern is defined as the minimum pre-destruction size (nm)' as an indicator of the pattern pour resistance, and the smaller the line width, the better. Further, the measurement of the size (nm) before the minimum is performed using a scanning electron microscope (trade name "S-9380" manufactured by Hitachi High-Tech Co., Ltd.). [Spot defect] The product name "CLEAN TRACK ACT8" (manufactured by Tokyo Electron Co., Ltd.) was used to prepare the processing conditions 1 0 0. (:, 6MDS (hexamethyldidecylamine) treated -68-200923579 8 inch wafer at 60 seconds. The linear composition of the sensitive radiation was spin coated on the 8 inch sand wafer. The cloth was baked (pb) under the conditions of Table 3 to form a photoresist film having a film thickness of 120 nm. Thereafter, an ArF excimer laser exposure apparatus (trade name "NSR S306C", Nicon) was formed on the photoresist film. System, lighting conditions; NAO.78 Sigma O.85), the film peeling without forming a reticle pattern, exposure for the optimum exposure in the sensitivity evaluation. Secondly, under the conditions shown in Table 3, after PEB, borrow The substrate was evaluated by a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C for 3 seconds, washed with water, and dried to prepare a substrate for spot defect (Blob defect) evaluation. The substrate for spot defect evaluation was prepared as a commercial product. The "KLA2351" (manufactured by KLA Tencor Co., Ltd.) was measured and evaluated as "good" when the detected spot defects were 200 or less. When the number of spots exceeded 200, it was evaluated as "poor". (Examples 2 to 4 and Comparative Examples) 1) In addition to the prescription shown in Table 3, each sensitive substance was prepared in the same manner as in Example 1. The radiation linear compositions were evaluated using the same. The evaluation results are shown in Table 4. [Table 4] Sensitivity (mJ/cm2) Resolution (_ Cross-sectional shape of the pattern LWR (nm) Minimum impaired size Spot defect Example 1 29.5 85 Good 6.2 46 Good J Example 2 29.5 85 Good 6.7 42 Good J Example 3 29.5 85 Good 6.5 49 Good Example 4 29.5 85 Good 6.2 46 Good One Comparative Example 1 30.5 90 Good 6.9 49 Bad -69- 200923579 The results shown in Table 4 show that the dry etching resistance and the L WR characteristics can be improved by using only the sensitive radiation linear composition of the present invention. Industrial Applicability The sensitive radiation linear composition of the present invention is particularly suitable for use in ArF excimer mines. The lithography step is used as a light source. Especially in the formation of fine patterns below 90 nm, 'further in the immersion exposure step, it can be excellent in image formation performance. 'LWR is smaller' pattern is excellent in pour resistance and rarely Chemically amplified type of photoresist for the pattern of defects. -70-

Claims (1)

200923579 X. Patent Application No. 1 · A sensitive radiation linear composition characterized by containing a polymer (A) and a sensitive radiation linear acid generator (B), the polymer (A) containing the following general formula (1_1) The repeating unit (1) shown, the following general formula (1 - 2 ), the repeating unit (2), and the repeating unit having an acid dissociable group (3); (1-1) (In the above general formulas (1-1) and (丨-2), Ri independently represents a hydrogen atom methyl group or a di-gas methyl group; in the above general formula (1-1), R2 represents carbon a linear or branched alkyl group having 1 to 12, a cycloalkyl group, an alkylcarbonyl group having 1 to 12 carbon atoms, or a hydroxyalkyl group; in the above general formula (1-2), X represents a single bond and a stretch a methyl group, a linear or branched alkyl group having 2 to 20 carbon atoms, or a divalent cyclic hydrocarbon group having 3 to 9 carbon atoms, and R3 represents a linear chain having 1 to 10 carbon atoms containing at least one fluorine atom. An alkyl group or a branched alkyl group or an alicyclic alkyl group having a carbon number of 3 to 10%. 2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ (In the above general formula (2), R4 represents a hydrogen atom, a fluorine atom group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear number 1 to a linear or branched alkoxy group, or a linear or alkoxycarbonyl group having a carbon number of 2 to 11, and R5 represents a linear or branched group having a carbon number of 1 to 10, and a linear or branched stereo group having a carbon number of 1 to 10. Or a linear, branched or cyclic alkanesulfonyl group of 2 to 11, and a straight or branched alkyl group having a carbon number of 1 to 10, a substituted or substituted phenyl group, or a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted divalent group having a carbon number of 2 to 1 Å formed by two R6 groups; k represents an integer, r represents an integer of 0 to 10, and X represents the following In the general formula (3 (6), the anion shown in the above (but, when χ is an anion of the following general formula (3), the two R6 are not bonded to form a carbon number of 2 to 1 〇 or unsubstituted 2 Price base));, hydroxy [〇 branch branch carbon number this unique combination 0~2) ~ replaced by (3) (4) (6) -72- 200923579 (In the above general formula (3) + or 整6 of the alkane or unsubstituted carbon, R7 represents a hydroquinone carbon number of 1 to 12 substitution or a fun, a fluorine atom, a ~ substituted Hydrocarbyl group, n show a number; again, the above general formula (4)... 8 I do not, I, 4) 'R* denotes a carbon number-based parent group, a theater-based curtain oxy group, and a 叱4 hydroxyalkyl group Substituting a hydrocarbon group of 1 to 12; in the case of a singularity, in the general formulas (5) and (6), R9 independently of each other represents a carbon number 〖~〗 〇 linear or branched A substituted or unsubstituted divalent group containing a fluorine atom-containing alkyl group or a two fluorine atom having 2 to 10 carbon atoms formed by bonding. -73- 200923579 The designated representative figure of the seven-eighth: (1) The representative representative of the case is: No (2), the representative symbol of the representative figure is a simple description: If there is no chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: none