TW201132655A - Radiation sensitive linear resin composition and method for forming photoresist pattern - Google Patents

Abstract

A radiation sensitive linear resin composition having excellent LWR and may not easily occur film reduction is provided. A radiation sensitive resin composition containing (A) polymer having the repeat unit represented by the following general formula (1) and acid dissociation groups, (B) radiation sensitive linear acid generating agent, and (C) polymer containing fluorine atoms is provided (where in the general formula (1), R.sup.1 represents a hydrogen atom and so on, and R.sup.2 represents a single bond and so on. R.sup.3 represents a trivalent organic group).

Description

201132655 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for forming a linear composition of a radiation sensitive resin and a photoresist pattern. More specifically, it relates to a method for forming a radiation sensitive linear resin composition and a photoresist pattern which can form a photoresist film having good line edge width roughness (LWR) after development and which is less likely to cause film reduction. [Prior Art] In the field of microfabrication for manufacturing integrated circuit components, in order to obtain a higher degree of integration, it is desirable to perform microfabrication at a level of 0.10 ΜΠ 1 or less (ie, Sub-Quarter Micron). The lithography etching technique, in which KrF excimer laser (wavelength 248nm) or ArF excimer laser (wavelength 193 nm) is attracting great attention. However, in the field of microfabrication, it is more desirable to form a finer photoresist pattern (for example, a fine photoresist pattern having a line width of about 45 nm), in order to form a finer photoresist pattern, for example, A process of shortening the wavelength of the light source of the exposure device or increasing the number of apertures (NA) of the lens is performed. However, in order to achieve a short wavelength of the wavelength of the light source, it is often problematic to use a new expensive exposure apparatus. Further, when the number of openings of the lens is increased, it is often necessary to select the resolution and the depth of focus. For example, when the resolution is increased, there is a problem that the depth of focus is lowered. Therefore, in recent years, in order to solve the above-mentioned problem of the lithography etching technique, for example, a report of a method such as an immersion exposure (liquid immersion lithography) method has been proposed -5-201132655. This method is a method of interposing a liquid for immersion exposure (for example, pure water, a fluorine-based inert liquid or the like) between a lens and a photoresist film (on a photoresist film) during exposure. According to this method, the exposure light path space filled with an inert gas such as air or nitrogen can be filled with a liquid having a refractive index (η) having a refractive index higher than that of air or the like, and even if the same exposure light source as in the related art is used, It is also possible to obtain the same effect as that obtained by shortening the wavelength of the light source of the exposure device, that is, high resolution can be obtained. Also, it does not cause a decrease in the depth of focus. Therefore, according to the immersion exposure method, the lens actually installed in the existing device can be used to form an excellent photoresist pattern with low cost, excellent resolution, and even better depth of focus. For the process, for example, a photoresist film formed by protecting a linear radiation-sensitive resin composition and an infiltrated exposure film formed on the wetted upper film formed on the photoresist film have been proposed (for example, Patent Document 1). Or a method of forming a photoresist film using a radiation-sensitive linear resin composition containing a fluorine atom-containing polymer for the purpose of removing the infiltrated upper film or the like (for example, Patent Document 2), and expecting it to achieve an increase in yield (ie, Improve the processing capacity). [PRIOR ART DOCUMENT] [Patent Document 1] International Publication No. 05/069076 (Patent Document 2) International Publication (KOKAI-A No. 6664 No. 201132655) [Problems to be Solved by the Invention] However, the above-mentioned In the case of using a radiation sensitive linear resin composition containing a fluorine atom-containing polymer, problems such as deterioration of LWR (Line Width Roughness) and film reduction of the photoresist pattern may occur after development. Therefore, it is urgent to develop a form which can be formed. A photosensitive radiation linear resin composition having a good LWR 'resistance of a photoresist film which is less likely to cause film reduction after development. The present invention has been made to solve the problems caused by the above prior art, and it is proposed to have a good development after development. LWR, a sensitive radiation linear resin composition of a photoresist film which is less likely to cause film reduction, and a method for forming a photoresist pattern using the same. [Means for Solving the Problem] The inventors have intensively studied to achieve the above problems. As a result, it was found that a polymer containing (A) specific repeating unit, and having an acid-dissociable group, and (B) a radiation-sensitive linear acid generator were used. And (C) a radiation-sensitive linear resin composition obtained by using a polymer containing a fluorine atom, the above problem can be easily attained, and the present invention has been completed. The present invention provides the following radiation-sensitive linear resin composition, and A method for forming a photoresist pattern. [1] A radiation sensitive linear resin composition comprising (A) a repeating unit represented by the following formula (1), and a polymer having an acid dissociable group' (B) a radiation-sensitive linear acid generator, and (c) a polymer containing a fluorine atom. 201132655 [Chem. 1]

(In the formula (1), R1 represents a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; and R2 represents a single bond, a divalent hydrocarbon group having a carbon number of 1 to 5, an alkanediyloxy group or an alkanediyl group; (2) The sensible radiation linear resin composition according to the above [1], wherein the repeating unit represented by the above formula (1) is the following formula (Id) Represented repeat unit, [Chemical 2]

(In the formula (1-1), R1 represents a hydrogen atom, a lower-grade or a lower alkyl group; R2 represents a single bond, a divalent hydrocarbon group having a carbon number of 1 to 5, an alkanediyloxy group or Alkyldicarbonyloxy; R5() represents a group of -8 to 201132655 represented by the following formula (a), or a group represented by the following formula (b);

(In the formula (a), 'nl represents an integer of 〇~2, and 'n2 to η5 in the formula (b) each independently represent an integer of 〇~2; in the formula (a) and the formula (b), * And a bond represented by the formula (a) and a group represented by the formula (b) are 'carbon atoms constituting the bases' At least one may be substituted by an oxygen atom, a nitrogen atom or a carbonyl group. Further, the group represented by the formula (a) and the group represented by the formula (b) may have a substituent) [3] as described above [2] The sensitive radiation linear resin composition, wherein the repeating unit represented by the above formula (1) is a repeating unit represented by the following formula (1-la), [Chemical 4]

(1-la) -9- 201132655 (In the formula (1-la), R1 represents a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; and R2 represents a single bond, a hydrocarbon group having a carbon number of 1 to 5; , alkanediyloxy, or alkanedicarbonyloxy; R51 is a group represented by the following formula (al), or a group represented by the following formula (bl);

(In the formula (al) and the formula (b1), * represents a bond bond of the R2 bond in the formula (Ι-la)) [4] The radiation-sensitive linear resin composition as described in the above [1] Wherein the '(C) polymer has at least one repeating unit selected from the group consisting of each repeating unit represented by the following general formulae (2-1) to (2_3), -10- 201132655 6]

(2-1) (2-2) (2-3) (In the formula (2-1) to (2-3), 'R1 represents a hydrogen atom, a lower alkyl group' or a halogenated lower alkyl group; In the formula -1), R9 represents a fluorinated alkyl group having a carbon number of 1 to 30; in the formula (2-2), 'R6 represents a single bond or a (g+Ι) valent bond group, and g is an integer of 1 to 3 In the formula (2-3), 'R7 represents a divalent bond group; in the formula (2-2) and the formula (2-3), 'R8 represents a hydrogen atom, an acid dissociable group, or an alkali dissociation property; The radical 'Rl() each independently represents a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 10 carbon atoms: further, all of R1() is not a hydrogen atom). [5] The radiation sensitive linear resin composition according to the above [4], wherein the (C) polymer oxime contains a group represented by the following formula (2-4) and a formula (hereinafter) ( 2-5) A repeating unit of at least one of the indicated groups (other than the repeating unit represented by the above formula (2_3) -11 - 201132655 [Chemical 7] NH II = S = 0 I COOH R11 (2 -4) (2-5) (In the formula (2-4), R11 represents a hydrocarbon group having a carbon number of 1 to 1 取代 which is substituted by a fluorine atom). [6] A linear composition of a radiation sensitive resin as described in the above [5] The content of the polymer (C) is 0.1 to 40 parts by mass based on 100 parts by mass of the polymer (A). [7] A method for forming a photoresist pattern, characterized in that it has the aforementioned The photosensitive radiation linear resin composition according to any one of [1] to [6], which is coated on a substrate to form a photoresist film forming step of the photoresist film, and is provided with an immersion exposure on the formed photoresist film. Exposure step of irradiating the photoresist film with radiation through the liquid of the aforementioned immersion exposure, in comparison with the use of the developer The above-mentioned photoresist film is developed to form a resistive pattern development step. [Effect of the Invention] The sensitive radiation linear resin composition of the present invention has a light which can form a good LWR after development and is less likely to cause film reduction. [Embodiment of the Invention] [Embodiment of the Invention] -12-201132655 Hereinafter, the embodiment of the present invention will be described, but the present invention is not limited to the following embodiments. That is, the scope of the present invention is not exceeded. It is also within the scope of the invention to add appropriate modifications, improvements, etc. to the following embodiments. [1] Sensitive radiation linear resin composition: The sensitive radiation linear resin composition of the present invention, (A) a repeating unit represented by the above formula (1) (hereinafter also referred to as "repeating unit (Ϊ)"), and a polymer having an acid dissociable group (hereinafter referred to as 'the same' "(A) polymer"), and (B) a radiation-sensitive linear acid generator (hereinafter, also referred to as "(B) acid generator"), and (C) contains a fluorine atom. The composition of the polymer (hereinafter, also referred to as "(C) polymer"). In the case of "Rx" in the general formula of the present specification, when the same content is expressed, The same number is used. [1-1] (A) Polymer: (A) The polymer is a repeating unit represented by the above formula (1), and an acid dissociable group which forms the linearity of the sensitive radiation of the present invention. The composition of the substrate in the resin composition. The term "substrate" means the composition of the film forming energy. The (A) polymer 'is dissociated from the acid dissociable group to form alkali solubility through the action of an acid. A substance which is alkali-insoluble or poorly soluble in alkali before dissociation of the acid-dissociable group. In addition, in the present specification, "insoluble or poorly soluble" refers to an alkali developing condition in which a photoresist pattern formed by using a photosensitive film composition of (A) polymer-sensitive radiation-13-201132655 resin composition is formed. Next, in the case where only the (A) polymer film of 100 nm was used instead of the photoresist film for development, the property of 50% or more of the initial film thickness remained after the shadow. [l-1-la] The repeating unit represented by the formula (1): R1 in the formula (1) is a hydrogen atom, a methyl group, a carbon number represented by R2 in the formula (1), and a carbon number of 1 to 5 ;; for example, a linear or branched carbon number of 1 to 5, such as -C Η 2 -, ethyl, 1,3 -propyl, 2,2-propyl, 1,4-butylene, 1, 3-butylene, 1,2-f The alkyl group of the alkanediyloxy group ~5 represented by R2 in the formula (1) is bonded to an oxygen atom. The basis. a hydrocarbon group of a β valence, for example, -CH2-, an extended ethyl '1,3-1,3-propyl group, a 2,2-propanyl group, a 1,4-butylene group, a 1,3-butylene group, a 〇* a divalent hydrocarbon group of a divalent alkyl group represented by R2 represented by R2 in the formula (1) and a carbonyloxy group bonded to a carbonyloxy group, for example, -C Η 2 -, an ethyl group 1,3, propyl, 2,2-propenyl, 1,4-tert-butyl, 1,3-butylene, and the like. In the general formula (1), 'R3' represents a trivalent organic group, such as a trivalent chain hydrocarbon group or a trivalent type having a cyclic hydrocarbon structure, and a film thickness of jin is used. A hydrocarbon group such as a hydrocarbon group having a valence of 2 is preferable. With 1,2-propyl, butyl and the like. For example, a carbon number of 1 is a compound of 1 to 5, and a base of 1, 2 -extended is a 1,2-butylene group, such as a carbon number. Carbon number 1 to 5 - a propyl group, a 1,2-group group, a 1,2-diene group, specifically, a group having a trivalent group having a ring structure of a heterotetra 14 - 201132655. These groups may be substituted by a hydroxyl group, a carboxyl group, a cyano group or the like. The repeating unit represented by the formula (1) is, for example, a repeating unit represented by the above formula (1-1), and the repeating unit represented by the formula (1-1) is represented by the above formula (Ι-la). The repeating unit is a preferred example. When the repeating unit is represented by the above formula (1 -1 a ), a photoresist film having a LWR after development and having a better stomach and a film reduction can be formed. Further, R5 in the formula (1-1). And R51 in the formula (Ι-la), as described above, one of the carbon atoms constituting the groups may be substituted by an oxygen atom, a nitrogen atom or a carbonyl group, or may have a substituent. The substituent is, for example, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a cyano group, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group or the like. The repeating unit (I) is, for example, each repeating unit represented by the following general formulae (3-1) to (3-21). Among these, from the viewpoint of producing a radiation sensitive linear resin composition which can form a more excellent LWR after development and a film resist which is less likely to cause film reduction, it is represented by the following general formula (3 - 1). The repeating unit and the repeating unit represented by the following formula (3-9) are preferred. Further, R1 in the following general formulae (3-1) to (3-21) represents a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group. -15- 201132655 【化8】

(3·1) (3-2) (3-3) (3-4) (3·5) (3-6) (3·7)

In the repeating unit represented by the above formula (3-1) to (3-21), the formulae (3-1) to (3-16) correspond to the repeating unit represented by the above formula (1-1) and the above The unit of the repeating unit represented by the formula (1 -1 a ). In particular, the above formula (3-4) to (3-7) represents a repeating unit in which R5() in the above formula (1-1) and formula (Ι-la) is substituted. (i.e., the case where the group represented by the formula (a) has a substituent) is a weight of -16 to 201132655. The repeating unit represented by the above formula (3-11) and (3-12) is a repeating unit corresponding to the case where the group represented by the formula (b) has a substituent, specifically, for example, carbon constituting R5 < Any unit in which an atom is replaced by an oxygen atom or a nitrogen atom. The repeating unit represented by the above formulas (3-13) to (3-16) is a repeating unit in the case where the group represented by the formula (b) has a substituent, and specifically, for example, a carbon constituting R5() Any one of the atoms is substituted by an oxygen atom, a nitrogen atom or a carbonyl group, and has a unit of a substituent. Further, the monomers which form the repeating unit (I) can be synthesized by a conventionally known method, specifically, for example, Tetrahedron Letters,

Vol. 27, No. 32 ρ· 3 74 1 (1 98 6), Organic Letters, Vol. 4,

The method described in No. 15 p.2561 (2002) is synthesized. [1 - blb] Other repeating units (a): (A) The polymer 'in addition to the repeating unit represented by the above formula (1), may also have other repeating units (a). The other repeating unit (a) is, for example, the repeating unit (II) to (VI) shown below. [l-1-lb-1] Repeating unit (II): The repeating unit (II) is represented by the following formula (4-1) to (4_7), and the repeating unit is expressed by the following formula: -17- 201132655 [Chemical 9] R1

R14 (4-1) (In the formula (4-1), R1 represents a M atom, a lower-grade or a halogenated lower alkyl group; and R12 to R14 represent a linear or branched carbon number of 1 to 4 independently of each other. An alkyl group or an alicyclic hydrocarbon group having a carbon number of 4 to 20, and R13 and R14 may be bonded to each other to form a divalent alicyclic hydrocarbon group having a carbon number of 4 to 20 or a derivative thereof.

In the general formulae (4-2) to (4-7), 'R1' represents a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group: in the formula (4-2), 'R15 represents a hydrogen atom or a carbon number of 1 to 4; A substituted or unsubstituted alkyl group, Ρ represents an integer of from 1 to 3. In the above formulae (4-5) and (4-6), R16 independently represents a hydrogen atom or a methoxy group. In the above formulae (4-3) and (4-4), R17 each independently represents a single bond or -CH2-, and m each independently represents 0 or 1» the above formula (4--18-201132655 4 ) and ( 4-6) wherein R18 independently represents an oxygen atom or _Cii2: an alkyl group having a carbon number of 丨~4 represented by R12 to Rm in the formula (4-1), for example, 'methyl, ethyl, η- Propyl, i-propyl, .n-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, and the like. The alicyclic hydrocarbon group ' and the R 13 and R 14 having a carbon number of 4 to 2 Å represented by R12 to Ri4 in the formula (4-1) are bonded to each other and form a carbon atom bonded to each other. An alicyclic hydrocarbon group having a carbon number of 4 to 20, for example, a bridged skeleton such as an adamantane skeleton, an ornidyl skeleton, a tricyclodecane skeleton or a tetracyclododecane skeleton, or a cyclobutane, a group having a cycloalkane skeleton such as cyclopentane, cyclohexane, cycloheptane or cyclooctane; and the group having one or more of, for example, a methyl group, an ethyl group, an η-propyl group, Substituted by a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms such as propyl, n-butyl, 2-methylpropyl, 1-methylpropyl or t-butyl. A group having an alicyclic skeleton or the like. Among the alicyclic hydrocarbon groups, those having an adamantane skeleton, a bicyclo [2.2.1] heptane skeleton, a cyclopentyl skeleton, a cyclohexyl skeleton, a cycloheptyl skeleton, and a cyclooctane The base skeleton is preferred. "-CR12R13R14" in the formula (4-1), specifically, for example, t-butyl, ln-(l-ethyl-1-methyl)propyl, ln-(l,l-dimethyl )propyl, ln-(l,l--•methyl)butyl, 1·η-(1,1-methyl)pentyl, 1-(1,1-diethyl)propyl, 1 -η-(1,1-diethyl)butyl, 1-η-(1,1-diethyl)pentyl, 1-(1-methyl)cyclopentyl, 1-(1-ethyl Cyclopentyl, propyl)cyclopentyl, propyl)cyclopentyl, 1-(1-methyl)cyclohexyl, 1-(1-ethyl)cyclohexyl' 1-( -19- 201132655 ln- Propyl)cyclohexyl, propyl)cyclohexyl, 1-{b-methyl-1-(2-anbornyl)}ethyl, 1-{1-methyl-1-(2-tetracyclodecyl)}B Base, 1-丨1-methyl-1-(1-adamantyl)fluorenylethyl, 2-(2-methyl) borneol, 2-(2-ethyl) borneol, 2-( 2-n-propyl) borneol, 2-(2-i-propyl) borneol, 2-(2-methyl)tetracyclononyl '2-(2-ethyl)tetracyclodecyl , 2-(2-n-propyl)tetracyclodecyl, 2-(2-i-propyl)tetracyclodecyl, 2-(2-methyl)adamantyl, 2-(2-ethyl Adamantyl, 2-(2-n-propyl)adamantyl, 2- (2-i -propyl)adamantyl or the group formed by the alicyclic ring is one or more or more, for example, methyl, ethyl, η-propyl 'i-propyl, η-butyl a group substituted with a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms such as 2-methylpropyl group, 1-methylpropyl group or t-butyl group. A monomer forming a repeating unit (II), for example, (meth)acrylic acid 2·methyladamantyl-2-yl ester, (meth)acrylic acid 2-methyl-3-hydroxyadamantyl-2-yl Ester, 2-ethyladamantyl-2-yl (meth)acrylate, 2-ethyl-3-hydroxyadamantyl-2-yl (meth)acrylate, 2-n (meth)acrylate -propyladamantyl-2-yl ester, 2-isopropylidenyl-2-yl (meth)acrylate, 2-methylbicyclo(2.2.1)heptane-2 -yl ester, 2-ethylbicyclo(2.2.1)heptan-2-yl (meth)acrylate, -8-methyltricyclo(5.2.1.02'6]nonane-8 -Base ester, 8-methyltricyclo(5.2.1.02,6)nonane-8-yl ester, (meth)acrylic acid-4-methyltetracyclo[6.2.13' 6.02'7]dodecyl-4-yl ester, (meth)acrylic acid-4-ethyltetracyclo[6.2.13,6.02,7]Te-20-201132655 Dialkyl-4-yl ester, (methyl ) 1-(bicyclo[2.2.1]hept-2-yl)-1-methylethyl acrylate, 1-(tricyclo[5.2.1.02'6]nonane-8-yl) (meth)acrylate -1-methylethyl ester, (A 1-(tetracycline [6.2.13'6.02'7] dodec-4-yl)-1-methylethyl acrylate, 1-(adamantan-1-yl)(meth)acrylate 1-methylethyl ester, 1-(3-hydroxyadamantan-1-yl)-1-methylethyl (meth)acrylate, 1,1-dicyclohexylethyl (meth)acrylate 1,1-di(bicyclo[2.2.1]heptan-2-yl)ethyl (meth)acrylate, 1,1-di(tricyclo[5.2.1.02'6]decane (meth)acrylate -8-yl)ethyl ester, 1,1-di(tetracyclo[6.2_13'6.02'7]dodecan-4-yl)ethyl (meth)acrylate, 1,1 (meth)acrylic acid - bis(adamantan-1-yl)ethyl ester, 1-methyl-1-cyclopentyl (meth)acrylate, 1-ethyl-1-cyclopentyl (meth)acrylate, (A) Base) 1-methyl-1-cyclohexyl acrylate, 1-ethyl-cyclohexyl (meth) acrylate, and the like. Among these monomers, 2-methyladamantyl-2-yl (meth)acrylate, 2-ethyladamantyl-2-yl (meth)acrylate, (meth)acrylic acid-2 -Methylbicyclo[2.2.1]heptan-2-yl ester, (meth)acrylic acid-2-ethylbicyclo[2.2.1]hept-2-yl, (meth)acrylic acid 1-(bicyclo[2.2 .1]hept-2-yl)-1-methylethyl ester, 1-(adamantan-1-yl)-1-methylethyl (meth)acrylate, 1-methyl (meth)acrylate 1--1-cyclopentyl ester, 1-ethyl-1-cyclopentyl (meth)acrylate, 1-methyl-1-cyclohexyl (meth)acrylate, 1-B (meth)acrylate Alkyl-1-cyclohexyl ester is preferred. The base group represented by R15 in the general formula (4-2) which may have a carbon number of 1 to 4 and taken from the group - 21, 201132655, for example, methyl, ethyl, n-propyl, k-propyl, and heart Butyl, 2-methylpropyl ' 1 methyl propyl, _ butyl and the like. The ratio of the repeating unit (II) is, in the case where the total repeating unit of the (Α) polymer is 100% by mole, preferably 丨5 to 8 5 mol%, and more preferably 25 to 75 mol%. Jia's 35~6〇% is especially good. When the above content ratio is less than 15 mol%, the contrast after dissolution (i.e., the portion which can be dissolved in the developing solution and the insoluble portion) is degraded, and the shape of the pattern is lowered (that is, the cross section cannot be obtained). It is a doubt about the rectangular photoresist pattern. Further, when it exceeds 85 mol%, the adhesion to the substrate cannot be sufficiently obtained, and there is a fear that the obtained photoresist pattern is peeled off from the substrate. [; l-l-lb-2] Repeating unit (III): The repeating unit (III) in the other repeating unit (a), for example, a repeating unit produced by the monomer shown below. Namely, the above monomer is, for example, (meth)acrylic acid-5-side oxo(oxo)-4-oxa(oxa)-tricyclo[4.2.1.03'7]non-2-yl ester, (methyl) 9-methoxycarbonyl-5-oxo-4-oxa-tricyclo[4.2.1.03'7]non-2-yl acrylate, 5-(oxy)-4-(oxy)-4-(ethyl) acrylate Oxa-tricyclo[5.2.1 ·03'8]non-2-yl ester, (meth)acrylic acid-10-methoxycarbonyl-5-sideoxy-4-oxa-tricyclic [5.2. 1.03'8]壬-2-yl ester, (meth)acrylic acid-6-o-oxy-7-oxa-bicyclo[3.2.1]oct-2-yl ester, methoxycarbonyl (meth)acrylate -6-Phenoxy-7-oxa-bicyclo[3.2.1]oct-2-yl ester, (meth)acrylic acid-7-c-oxy-8-oxa-bicyclo[3.3.1]- 2-Based ester, (meth)acrylic acid 4-methoxycarbonyl-7-sideoxy-8-oxa-bicyclo[3.3.1-22-201132655]oct-2-yl ester, (methyl) 2-oxo-tetrahydropyran-4-yl acrylate, 4-methyl-2-oxotetrahydropyran-4-yl (meth)acrylate, (methyl)propionic acid 4-ethyl-2-oxo-tetrahydropyran-4-yl ester, (meth)acrylic acid _4·propyl-2-side oxygen Tetrahydropyran-4-yl ester, 5-(oxy)tetrahydrofuran-3-yl (meth)acrylate, 2,2-dimethyl-5-oxo-tetrahydrofuran (meth)acrylate- 3_based ester, (meth)acrylic acid-4,4-dimethyl-5-sided oxytetrahydrofuran-3-yl ester, (meth)acrylic acid-2-oxotetrahydrofuran-3-yl ester, ( Methyl)acrylic acid-4,4·dimethyl-2-oxooxytetrahydrofuran-3-yl, (meth)acrylic acid-5,5-dimethyl-2-oxooxytetrahydrofuran-3 -yl ester, (meth)acrylic acid 2_sideoxytetrahydrofuran-3 yl ester, (meth)acrylic acid-5-sided oxytetrahydrofuran-2-ylmethyl ester, (methyl)-propionic acid- 3,3-Dimethyl-5-oxo-tetrahydrofuran-2-ylmethyl ester, (meth)acrylic acid-4,4-dimethyl-5-oxo-tetrahydrofuran-2-ylmethyl ester, etc. . The ratio of the repeating unit (III) is preferably in the case where the total repeating unit of the (A) polymer is 100% by mole, preferably 〇 5 5 〇 耳 %, and preferably 20 to 40 摩尔 %. . When the content ratio is less than 10 mol%, the adhesion to the substrate may be insufficient, and the pattern may be peeled off. Further, when it exceeds 50 mol%, the solubility in the alkali developing solution may be insufficient, and the development defect may be increased. [Bu-l-3-3] repeating unit (IV): Repeat unit (IV) in other repeating units (a), for example, repeating units having an alicyclic hydrocarbon group of -23-201132655. The repeating unit having an alicyclic hydrocarbon group is, for example, a repeating unit represented by the following formula (5). [1 1]

(In the formula (5), R1 represents a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; and R19 represents an alicyclic hydrocarbon group having 4 to 20 carbon atoms). An alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R19 in the formula (5), for example, cyclobutane, cyclopentane, cyclohexane, bicyclo[2.2.1]heptane, bicyclo[2.2.2 Octane, tricyclo[5.2.1.0''6]nonane, tetracyclo[6.173,6.02,7]dodecane, tricyclo[3.3.1.13,7]decane, etc. The hydrocarbon group formed by the alicyclic ring produced or the like. The alicyclic ring derived from a cycloalkane may have a substituent, and for example, one or more or more methyl, ethyl, η-propyl, i-propyl, η-butyl may be used. The base group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like are substituted with a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms. These contents are not limited to those substituted by the above alkyl group, and may be substituted by a hydroxyl group, a cyano group, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group or oxygen. A monomer which can form a repeating unit (IV), for example, (meth)acrylic acid-bicyclo[2.2.1]hept-2-yl ester, (meth)acrylic acid bicyclo[2.2.2]oct-2-yl ester , (meth)acrylic acid-tricyclo[5.2.1. 〇2'6] -24- 201132655 癸-7-yl ester '(meth)acrylic acid-tetracyclo[6.173,6.〇2,7]12院 9-yl ester, (meth)acrylic acid-tricyclo[3.3.1.13,7]non-1-yl ester, (meth)acrylic acid tricyclo [3.3.1.I3,7]癸-2- Base ester and the like. The content of the repeating unit (IV) is preferably in the range of 3 〇 mol% or less when the total repeating unit of the (Α) polymer is 1.0% by mole, and more preferably 25 mol% or less. When the content ratio exceeds 3 〇 mol%, there is a concern that the shape of the photoresist pattern is deteriorated and the resolution is lowered. [l-l-lb-4] repeating unit (V): a repeating unit (V) in the other repeating unit (a), for example, a repeating unit represented by the following formula (6). [1 2]

(In the formula (6), R1 represents a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; and R2C> represents a divalent organic group). The divalent organic group represented by R2G in the formula (6) is preferably a divalent hydrocarbon group, more preferably a chain or cyclic hydrocarbon group, and may be an alkanediol group or a stretching group. Alkyl ester group. a divalent organic group represented by R2(), specifically, a propyl group, a tetramethyl group such as -CH2-, an ethylidene group, a 1,3-propanyl group or a 1,2-propanyl group , five-extension methyl, six-extension methyl, seven-extension methyl, eight-extension methyl, nine-extension methyl-25- 201132655, ten-extension methyl, eleven-extension methyl, twelve-extension methyl, thirteen-extension Methyl, fourteen methyl, fifteen methyl, sixteen methyl, seventeen methyl, eighteen methyl, nineteen methyl, icosylene, 1-methyl-1,3 - propyl, 2-methyl 1,3-propanyl, 2-methyl-1,2-propanyl, 1-methyl-1,4-butylene, 2-methyl-1, a 4-butyl group, a methylene group, an ethylene group, a propylene group, or a saturated chain hydrocarbon group such as a 2-propylene group, a cyclobutyl group such as a 1,3-cyclobutylene group, or a 1,3-butyl group. a cycloalkyl group having a carbon number of 3 to 10, such as a cyclopentyl group such as a pentyl group, a 1,4-cyclohexyl group or the like, a cyclopentyl group such as a 1,5-cyclooctyl group or the like. Or a monocyclic hydrocarbon ring group, a 1,4-extension borneol group or a 2,5-extension borneol base, etc., a 1,5-adamantyl group, a 2,6-exetadamantyl group, etc. 2 to 4 ring carbon such as adenine 4~30 hydrocarbon ring group of the crosslinked cyclic hydrocarbon ring group. Further, in the case of containing a divalent aliphatic cyclic hydrocarbon group of R2C), a spacer is provided between the bistrifluoromethyl-hydroxy-methyl group and the above divalent aliphatic cyclic hydrocarbon group. The alkylene group having 1 to 4 carbon atoms is preferred. Further, the divalent organic group represented by R2 () is preferably, for example, a hydrocarbon group containing a 2,5-extension borneol group, a 1,2-extended ethyl group, a propyl group or the like. a monomer forming a repeating unit (V), for example, (meth)acrylic acid (1,1,1·trifluoro-2-trifluoromethyl-2-hydroxy-3-propyl) ester, (meth)acrylic acid (1,1,1-Trifluoro-2-trifluoromethyl-2-hydroxy-4-butyl)ester, (meth)acrylic acid (1,1,1-trifluoro-2-trifluoromethyl- 2-hydroxy-5-pentyl)ester, (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-pentyl) (meth)acrylate, (meth)acrylic acid 2 -{[5-(l,,l',l,-trifluoro-2'-trifluoromethyl-2'-hydroxy)propyl]bicyclo[2.2.l]heptyl} ester, (A-26- 201132655 base) Aromatic acid 3-{[8-(1,1,1,-trifluoro-2,-trifluoromethyl-2,-hydroxy)propyl]tetracycline [6.173,6.〇2 , 7] dodecyl} ester and the like. The content ratio of the repeating unit (V) is preferably 30% by mole or less in terms of the total repeating unit of the (A) polymer being 100% by mole, and more preferably 25 % by mole or less. When the content ratio exceeds 3 〇 mol%, there is a fear that the formed photoresist film is more likely to be swollen by the alkali developer. [l-l-lb-5] repeating unit (VI): the repeating unit (VI) in the other repeating unit (a), such as the repeating unit produced by the aromatic compound. a monomer which forms a repeating unit produced by an aromatic compound, for example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxy Styrene, 3-methoxystyrene, 4-methoxystyrene, 4-(2-t-butoxycarbonylethyloxy)styrene 2-hydroxystyrene, 3-hydroxybenzene Ethylene, 4-hydroxystyrene, 2-hydroxy-α-methylstyrene, 3-hydroxy-α-methylstyrene, 4-hydroxy-α-methylstyrene, 2-methyl-3-hydroxybenzene Ethylene, 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxystyrene, 2-methyl-4-hydroxystyrene, 3-methyl-4-hydroxystyrene, 3,4- Dihydroxystyrene, 2,4,6-trihydroxystyrene, 4-1-butoxystyrene '4 small butoxy-«-methylstyrene, 4-(2-ethyl-2-propoxy) ) styrene, 4-(2-ethyl-2-propoxy)·α-methylphenylethylene, 4-(1-ethoxyethoxy)benzene, 4·(1·ethoxy B Oxy) _ α-methyl styrene, phenyl (meth) acrylate, (meth) acrylate -27- 201132655 benzyl, decene, 5-hydroxy decene, fluorene-vinyl naphthalene, 2 - vinyl Naphthalene , 2_ hydroxy-6-vinylnaphthalene, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, decyl (methyl) Acrylate, 2-mercapto (meth) acrylate, 9-fluorenyl (meth) acrylate, 9-fluorenylmethyl (meth) acrylate, fluorene-vinyl hydrazine, and the like. The content of the repeating unit (VI) is preferably in the range of 40% by mole or less, more preferably 30% by mole or less, in the case where (a) the total repeating unit of the polymer is 100% by mole. When the content ratio exceeds 4 〇 mol%, the transmittance of the radiation is lowered in the formed photoresist film, so that the appearance of the pattern is deteriorated (the shape of the pattern after development cannot be formed into a rectangle). doubt. Further, each of the above-mentioned repeating units (II) to (VI) may be contained alone or in combination of two or more. [1-1-2] Acid dissociable group: The acid dissociable group means a group obtained by substituting a hydrogen atom in a polar functional group such as a hydroxyl group or a carboxyl group, and is capable of dissociating in the presence of an acid. The acid dissociable group, specifically, for example, t-butoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, (thiotetrahydropyranylsulfonyl)methyl, (thiotetrahydrofuranylsulfonyl) a methyl group, or an alkoxy group substituted methyl group, an alkylsulfonyl group substituted methyl group or the like. Further, the alkoxy group is substituted with an alkoxy group (substituted group) in the methyl group, for example, an alkoxy group having 1 to 4 carbon atoms. Further, the alkylsulfonyl group is substituted with an alkyl group (substituent) in the methyl group, for example, an alkyl group having 1 to 4 carbon atoms. -28- 201132655 Further, the acid dissociable group is represented by a group represented by the formula "-C(R)3" or the like. Further, three R's represent a linear or branched alkyl group having a carbon number of 1 to 4 independently, a monovalent alicyclic hydrocarbon group having a carbon number of 4 to 20, or a group derived from the above. Any two R's are bonded to each other, and each of the carbon atoms bonded to the bond forms a divalent alicyclic hydrocarbon group having a carbon number of 4 to 20 or a group derived therefrom, and a residual R represents a carbon number. A linear or branched alkyl group of 1 to 4, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a group derived therefrom. a linear or branched alkyl group having 1 to 4 carbon atoms represented by R in the group represented by the formula "-C(R)3", for example, methyl group, ethyl group, η-propyl group, i -propyl, η-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, etc., carbon represented by R in the group represented by the formula "-C(R)3" a monovalent alicyclic hydrocarbon group of 4 to 2 Å, for example, norbornane, tricyclodecane, tetracyclododecane, adamantane, or cyclobutane, cyclopentane, cyclohexane, cycloheptane And a group formed by an alicyclic ring produced by a cycloalkane or the like, such as cyclooctane. Further, the group derived from the above alicyclic hydrocarbon group, for example, the above monovalent alicyclic hydrocarbon group is one or more or more, for example, methyl, ethyl, η-propyl, i-propyl, n. a group substituted with a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms such as a butyl group, a 2-methyl group, a fluorene-methylpropyl group or a t-butyl group. Among the above, the alicyclic hydrocarbon group having a carbon number of 4 to 20 represented by R is an ornidyl, tricyclodecane, tetracyclododecane, adamantane, cyclopentane or cyclohexane. The alicyclic hydrocarbon group formed by the resulting alicyclic ring is preferably a group in which the -29 - 201132655 alicyclic hydrocarbon group is substituted by an alkyl group. Any two Rs represented by R in the group represented by the formula "-C(R)3" are bonded to each other, and carbon atoms are formed simultaneously with the carbon atoms (carbon atoms bonded to the oxygen atom) bonded thereto. The alicyclic hydrocarbon group having a valence of 4 to 20, for example, a monocyclic hydrocarbon group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group; an exo-norbornyl group; a tricyclodecane A polycyclic hydrocarbon group such as a tetracyclic alkylene group or a crosslinked polycyclic hydrocarbon group such as an adamantyl group. Further, any two Rs represented by R in the group represented by the formula "-C(R)3" are bonded to each other, and each of them forms a carbon number of 4 to 20 carbon atoms together with the bonded carbon atoms. The group derived from the cyclic hydrocarbon group, for example, the above-mentioned divalent alicyclic hydrocarbon group is one or more or more, for example, methyl, ethyl, η-propyl, i-propyl, n-butyl, A group substituted with a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms such as 2-methylpropyl group, 1-methylpropyl group or t-butyl group. Among these, a monocyclic hydrocarbon group such as a cyclopentyl group or a cyclohexyl group or a group in which a divalent alicyclic hydrocarbon group (monocyclic hydrocarbon group) is substituted by an alkyl group is preferred. Wherein, the group represented by the formula "-C(R)3", specifically, for example, t-butyl, 1-n-(1-ethyl-1-methyl)propyl, ln-(1) 1-dimethyl)propyl, ln-(l,l-dimethyl)butyl, dimethyl)pentyl, 1-(1,1-diethyl)propyl, ln-(l,l -diethyl)butyl, 1-n-(l,l-diethyl)pentyl, •methyl)cyclopentyl, fluorenyl-(1-ethyl)cyclopentyl, 1-(ln-propyl Cyclopentyl, propyl)cyclopentyl, 1·(1-methyl)cyclohexyl, 1-(1-ethyl)cyclohexyl, 1-( -30- 201132655 ln-propyl)cyclohexyl, ^(丨-丨·propyl)cyclohexyl, 1{1 methyl·1-(2-arbornyl)}ethyl, 丨 甲基 methyl-丨-^-tetracyclononyl)}ethyl, 1 -{1-methyladamantyl) fluorenylethyl, 2·(2·methyl) ornitonyl, 2 - (2-ethyl) ornithyl, 2 _ ( 2 η η propyl) Insulinic acid alkyl, 2-(2-i.propyl) probornopyl, 2_(2-methyl)tetracyclononyl, 2-(2-ethyl)tetracyclononyl, 2_(2n-propyl Tetracyclic fluorenyl, 2-(2-i-propyl)tetracyclodecyl, 1-(1-methyl)adamantyl, 1-(1-ethyl)adamantyl, 丨_ (丨_ n _ propyl) adamantyl, 1-( Ι-i-propyl)adamantyl, or a group formed by the alicyclic ring is one or more or more, for example, a methyl group, a linear, branched or cyclic carbon number of 1 to 4 such as ethyl, n-propyl, i-propyl, η-butyl, 2-methylpropyl, 丨-methylpropyl or t-butyl The group substituted with an alkyl group is equivalent to the group represented by the formula "-C(R)3", t-butoxycarbonyl group or alkoxy-substituted methyl group among the acid dissociable groups. good. [1-1-3] Content ratio of fluorine atom: (A) The polymer may contain a fluorine atom, may not contain a fluorine atom, and may contain a fluorine atom with respect to the fluorine atom in the (C) polymer. The content ratio of the fluorine atom is smaller. (A) The content ratio of the fluorine atom in the polymer 'in the case where the total amount of the (A) polymer is 1% by mass, usually less than 5% by mass' - generally 0 to 4.9 % by mass Good, with 〇~4.0% by mass as better. (A) The content ratio of fluorine atoms in the polymer is smaller than that in the (C) polymer' (c) Poly-31 - 201132655 The composition tends to favor the surface layer of the photoresist film. Therefore, the water repellency of the surface layer portion of the formed photoresist film can be improved, and the advantage of forming a photoresist film having good water repellency can be formed without separately forming an underlayer film during immersion exposure. Further, the ratio of the fluorine atoms of the (A) polymer to the (C) polymer is preferably 1% by mass or more. When the difference is 1% by mass or more, the (C) polymer tends to tend to be on the surface of the photoresist film. In addition to the (A) polymer, when the polymer (C) described later is contained, a radiation sensitive resin composition which is particularly suitable for forming a photoresist film in the immersion exposure can be obtained. Specifically, for example, when (A) the polymer contains a fluorine atom, as described above, the content ratio of the fluorine atom in the (A) polymer is smaller than the content ratio of the fluorine atom in the (C) polymer. The content of the fluorine atom is smaller than when the side of the (A) polymer is smaller than the (C) polymer, and based on the oil repellency of the (C) polymer when the photoresist film is formed ( C) The polymer has a tendency to be highly distributed in the surface of the photoresist film. That is, the (C) polymer tends to be on the surface of the photoresist film (the side on which the liquid for immersion exposure is disposed). Therefore, it is not necessary to separately provide an overlayer film for blocking the photoresist film and the wetting medium, and therefore it is suitable for use in an immersion exposure method. Here, the content ratio of the fluorine atom in the present specification is ruthenium measured by 13C-NMR. (A) The weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) method of the polymer is not particularly limited, and is generally preferably 1,000 to 1,000,000, and more preferably 1,000 to 30,000. Preferably, it is 1,000 to 20, and 〇〇〇 is particularly good. When the above Mw is less than 1,000, there is a fear that the heat resistance of the formed photoresist film is lowered. Further, when it exceeds -32 - 201132655 1 00,000, there is a fear that the developability of the formed photoresist film is lowered. Further, the ratio (Mw/Mn) of the Mw obtained by the GPC method to the number average molecular weight (??) is usually from 1 to 5, preferably from 1 to 3. Further, in the (A) polymer, the ratio of the low molecular weight component derived from the monomer used in the actual production of the (A) polymer is the solid content, and the total amount of the (A) polymer is 1 〇. In the case of 〇% by mass, it is preferably 0.1% by mass or less, more preferably 7% by mass or less, and most preferably 0.05% by mass or less. When the content ratio is 〇. 1% by mass or less, the amount of eluted matter dissolved in the immersion exposure liquid at the time of immersion exposure can be reduced. In addition, it is possible to prevent the occurrence of foreign matter during storage, and to prevent the occurrence of coating spots during coating, so that the occurrence of defects during formation of the photoresist pattern can be sufficiently suppressed. The above-mentioned low molecular weight component derived from a monomer is a component of Mw500 or less, for example, a monomer, a dimer, a trimer, an oligomer, or the like. The method for removing the components below MW500 (that is, the method for purifying the polymer (A)) may be, for example, a chemical purification method such as water washing or solution extraction, or a chemical purification method, a critical filtration method, a centrifugal separation method, or the like. A combination of physical refining methods and the like. Further, the above-mentioned low molecular weight component derived from the monomer in the polymer (A) can be detected by high-speed liquid chromatography (HPLC). Further, it is preferable that the (A) polymer has a smaller content of impurities such as a halogen or a metal. When the content of the above impurities is small, the sensitivity, resolution, process stability, and the like of the formed photoresist film can be further improved, and a good photoresist pattern shape can be obtained. (A) a polymer, for example, a monomer (polymerizable unsaturated monomer) used for forming the above-mentioned respective repeating units, -32-201132655, using hydrogen peroxide, a dialkyl peroxide, or a hydrazine The radical polymerization initiator such as a base peroxide or an azo compound is produced by, if necessary, polymerization in a suitable solvent in the presence of a chain shifting agent. The solvent used in the above polymerization, for example, an alkane such as η-pentane, η-hexane, η-heptane, η-octane, η-decane or η-decane; cyclohexane or cycloheptane Ring-ring oximes such as phenyl, toluene, xylene, ethylbenzene, cumene, etc.; chlorobutanes, bromohexanes, etc. Halogenated hydrocarbons such as dichloroethane, hexamethyldibromide and chlorobenzene; saturated residual acid vinegar such as ethyl acetate, η-butyl acetate, i-butyl acetate, methyl propionate; acetone, 2 a ketone such as butanone, 4-methyl-2-pentanone or 2-heptanone; an ether such as tetrahydrofuran, dimethoxyethane or diethoxyethane; methanol, ethanol, 1 An alcohol such as propanol, 2-propanol or 4-methyl-2-pentanol. These solvents may be used singly or in combination of two or more kinds. The reaction temperature at the time of polymerization is usually 40 to 150 ° C, preferably 50 to 12 ° C. The reaction time is usually from 1 to 4 8 hours, preferably from 1 to 24 hours. [1 - 2] (B) Sensitive radiation linear acid generator: (B) The radiation sensitive linear acid generator is a substance which generates an acid by irradiation with light such as radiation (hereinafter also referred to as "exposure"). Subsequently, the acid dissociable group present in the (A) polymer is dissociated from the (A) polymer by the action of the acid produced by the (B) acid generator by exposure. Subsequently, the (A) polymer which is dissociated by the acid dissociable group after -34-201132655 forms alkali solubility. That is, the exposed portion of the photoresist film is easily soluble in the alkali developing solution. Subsequently, the development result is carried out via an alkali developing solution to form a positive resist pattern. The above (B) acid generator is, for example, a compound described in paragraphs [0800] to [0113] of JP-A-2000-135040. Further, the (B) acid generator may be used singly or in combination of two or more. (B) The content of the acid generator is preferably 〇1 to 30 parts by mass, more preferably 2 to 27 parts by mass, based on 100 parts by mass of the (A) polymer, and more preferably 5 to 2 parts by mass. It is especially good. When the above content is less than 0.1 part by mass, the sensitivity and resolution of the formed photoresist film may be lowered. On the other hand, when it exceeds 30 parts by mass, the coating property and pattern shape of the formed photoresist film may be lowered. [1-3] (C) Polymer: (C) The polymer is a component of the polymerizable radiation linear resin composition of the present invention as a polymer additive, which is a polymer containing a fluorine atom. When the polymer is contained, the formed photoresist film can have good water repellency, and the immersion exposure step can be used without exposure to the infiltrated upper film. Further, the inclusion of the (A) polymer and the (C) polymer result allows the (C) polymer to be biased toward the surface of the photoresist film to obtain good water repellency. (C) The polymer 'as described above is not particularly limited as long as it is contained before the fluorine atom is contained in the molecule, and is represented by the following formula (2 -1 ) -35-201132655. There is also a case called "repeating unit (2 -1 )"), and a repeating unit represented by the following formula (2-2) (hereinafter, also referred to as "repetitive unit (2-2)"), It is preferable that at least one of the repeating units selected from the group formed by the repeating unit represented by the following formula (2-3) (hereinafter, also referred to as "repeating unit (2-3)") is preferable. With such a repeating unit result, it is possible to suppress the (B) acid generator or the acid diffusion controlling agent in the resist film from being dissolved in the immersion exposure liquid. In addition, since the contact angle (increased) of the photoresist film and the immersion exposure liquid can be increased, water droplets generated by the immersion exposure liquid are less likely to remain on the photoresist film, and the immersion exposure can be suppressed. The occurrence of defects as a cause. 【化1 3】

(2-1) (2-2) (2-3) (In the formula (2-1) to (2-3), R1 represents a hydrogen atom, a lower alkyl group, or a dentated lower alkyl group; In 2-1), R9 represents a fluorinated alkyl group having a carbon number of 1 to 30; in the formula (2-2), R6 represents a single bond or a (g+Ι) valent bond group, and g is 1 to 3 In the formula (2-3), R7 represents a bond group of divalent-36-201132655; in the formula (2-2) and formula (2-3), R8 represents a hydrogen atom and an acid dissociable group. The 'or alkali dissociable group' each independently represents a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having a carbon number of 1 to 1 Å. Further, all of R10 are not a hydrogen atom. [1-3-1] The repeating unit represented by the formula (2-1): a lower alkyl group represented by R1 in the formula (2-1), for example, a methyl group or the like. A halogenated lower alkyl group represented by R1 in the formula (2-1), for example, a trifluoromethyl group or the like. A fluorinated alkyl group having 1 to 30 carbon atoms represented by R9 in the formula (2-1), for example, a linear or branched carbon number of 1 to 6 substituted with at least one or more fluorine atoms An alkyl group, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, which is substituted by at least one fluorine atom, or a group derived therefrom, which is substituted with at least one fluorine atom. a linear or branched alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-(2-methyl) Propyl), 1-pentyl, 2-pentyl, 3-pentyl, 1-(2-methylbutyl), 1-(3-methylbutyl), 2-(2- Methylbutyl), 2-(3-methylbutyl)-p-pentyl, 1-hexyl, 2-hexyl, 3-hexyl, 1-(2-methylpentyl), 1-( 3-methylpentyl), 1-(4-methylpentyl), 2-(2-methylpentyl), 2-(3-methylpentyl), 2-(4- a partially fluorinated or perfluoroalkyl group of a linear or branched alkyl group such as methylpentyl), 3-(2-methylpentyl) or 3-(3-methylpentyl) Wait. Further, the alicyclic hydrocarbon group having a carbon number of 4 to 20, which is substituted by at least one fluorine atom, or a group derived therefrom, for example, a cyclopentyl group or a cyclopentylmethyl group , 1-(1-cyclopentylethyl), 1-(2-cyclopentylethyl), cyclohexyl, cyclohexylmethyl, 1-(1-cyclohexylethyl), 1-( 2-cyclohexylethyl), cycloheptyl, cycloheptylmethyl, 1-(1-cycloheptylethyl), 1-(2-cycloheptylethyl), 2-originyl, etc. A partially fluorinated or perfluoroalkyl group of the alicyclic alkyl group. A monomer which can form a repeating unit represented by the formula (2 -1 ), for example, trifluoromethyl (meth) acrylate ' 2,2,2-trifluoroethyl (meth) acrylate, perfluoroethane (meth) acrylate, perfluoro n-propyl (meth) acrylate vinegar, perfluoro i-propyl (meth) propionate, perfluoro n-butyl (meth) acrylate , perfluoro i-butyl (meth) acrylate, perfluoro t-butyl (meth) acrylate, (^^^hexafluoropropyl) (meth) acrylate, 1- (2, 2 ,3,3,4,4,5,5-octafluoropentyl)(meth)acrylate, perfluorocyclohexylmethyl(meth)acrylate,丨_( 2,2,3,3,3 -pentafluoropropyl)(meth)acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,1〇,1〇,1〇- Heptadecyl sulfhydryl) (meth) acrylate, 1-( 5-trifluoromethyl_3,3,4,4,5,6,6,6-octafluorohexyl) (meth) acrylate, etc. 》 The ratio of the repeating unit (2-1) is 'in the case of (c) the total repeating unit of the polymer is 100 mol%, preferably 2 〇 to 9 〇 mol%, and 20 to 80 mol% For better, it is especially good for 2〇~7〇%. When the content ratio is within the above range, it is advantageous in the formed photoresist film to have a balance between water repellency and affinity for the developer -38-201132655. [1-3-2] The repeating unit represented by the formula (2-2): a (g + 1 )-valent bond group represented by R6 in the formula (2-2) Specifically, for example, a carbon number a hydrocarbon group of 1 to 3 Å (g + Ι), or a combination of the same with an oxygen atom, a sulfur atom, an imine group, a mineral group, -CO-0 - or -CO-NH- Construction, etc. Further, g is an integer of 1 to 3, and g is 2 or 3. The structures represented by the following formula (2-2a) in the formula (2-2) are independent of each other. [it 14] R10 -(2-2a) OR8 A hydrocarbon group having a (g+1) valence of 1 to 30, having a chain structure of R6, for example, methane, ethane, propane, butane, 2 -Methylpropane, pentane, 2-methylbutane, 2,2-dimethylpropane, hexane, heptane, octane, decane, decane, etc. (g + Ι) a structure obtained by hydrogen atoms. Further, R6 of the cyclic structure is, for example, cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.02'6] a structure obtained by removing (g + Ι) hydrogen atoms from a condensed hydrocarbon having 4 to 20 carbon atoms such as decane or tricyclo[3.3.1.13'7] decane; and an aromatic group having 6 to 30 carbon atoms such as benzene or naphthalene The structure obtained by removing (g + Ι) hydrogen atoms by hydrocarbons is equivalent to 构造R6, and the hydrocarbon group is combined with an oxygen atom, a sulfur atom, an imine group, a carbonyl group, -39 - 201132655 -CO-O- or -CO-NH- The structure is, for example, a structure represented by the following general formula or the like. Further, in the following formula, 'R21 each independently represents a single bond, a chain hydrocarbon group having a carbon number of 1 to 1 fluorene, a cyclic hydrocarbon group having a carbon number of 4 to 20, or a carbon number of 6 to 30. Aromatic hydrocarbon group. g is an integer from 1 to 3; [Chemical 1 5]

a chain hydrocarbon group having a carbon number of 1 to 10 represented by R21 in the above formula, for example, methane, ethane, propane, butane, 2-methylpropane, pentane, 2-methylbutane, A group derived from 2,2-dimethylpropane, hexane, heptane, octane, decane, decane, or the like. a cyclic hydrocarbon group having a carbon number of 4 to 20, for example, cyclobutane, cyclopentane, cyclohexane, bicyclo[2.2.1]heptane, bicyclo[2.2.2].octane' tricyclic [5 ·2_1.02'6] The base generated by brothel, tricyclic [3.3.1_13'7] decane, etc. The aromatic hydrocarbon group having a carbon number of 6 to 3 Å is, for example, a group derived from benzene, toluene, xylene, ethylbenzene or cumene. Further, 'R61 may also have a substituent 'substituent, for example, methyl, ethyl, η-propyl, i-propyl, η-butyl, 2 - from ganyl propyl, 201132655 1-methyl propyl A linear or branched alkyl group having a carbon number of 1 to 4 such as a group or a t-butyl group. The acid dissociable group represented by R8 in the formula (2-2), and the acid dissociable group in the polymer of (A) are exemplified by the same. When the acid dissociable group is present, the solubility of (C) present in the exposed portion can be improved. It is presumed that the effect of the formation of a polar group by the acid generated by the exposure step and the acid-dissociable group of the (C) polymer in the formation step of the photoresist pattern described later. The base dissociable group represented by R8 in the formula (2-2) may be a group which can be dissociated in the presence of a base obtained by a hydrogen atom in a polar functional group such as a hydroxyl group or a carboxyl group. The base dissociable group is not particularly limited as long as it is of the nature described above, and is, for example, a group represented by the following formula (2), or a cyclic group as in the above-mentioned polymer method. Reaction, such as, taken, and has a -2al) Ο

(In the formula (2-2al), R22 represents a hydrocarbon group in which at least one hydrogen atom is substituted with a carbon number of 1 to 10) R22 in the formula (2-2al), which is a total atom of a hydrogen atom of a hydrocarbon group The substituted linear or branched carbon number of 1 to 1 fluorene is preferably a trifluoromethyl group. In the repeating unit (2-2), for example, the repeating unit represented by the following formula, the repeating unit represented by the following formula (7-2), and the fluorine atomic moiety are (7-1). -41 - 201132655

(In the formulae (7-1) and (7-2), R1 represents a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group, and R24 represents a hydrogen atom, an acid dissociable group, or an alkali dissociable group. In 7-1), R23 represents a bond group of (g + 1 ) valence. In the formula (7-2), g is an integer of 1 to 3), and a repeating unit represented by the above formula (7-1) is formed. In addition, the compound represented by the following formula (7-2), specifically, a compound represented by the following formula, and the like. Further, in the following formula, R1 represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and R24 represents a hydrogen atom, an acid dissociable group or an alkali dissociable group. -42- 201132655 【化1 8】

For example, the compound wherein R24 in the above formula is an acid-dissociable group or an alkali-dissociable group can be obtained by using a compound in which each of the above formulas is a hydrogen atom. Specifically, for example, in the case where the compound represented by the above formula (2-2al) is synthesized, a compound in which R24 is a hydrogen atom in the above various formulas is condensed with a fluorocarboxylic acid in the presence of an acid to carry out The esterification method or a conventionally known method such as a method of condensing a fluorocarboxylic acid halide with a carboxylic acid halide in the presence of a base. Further, a fluorinated alkyl group having 1 to 10 carbon atoms represented by R1Q in the formula (2-2), for example, a carbon number of 1 to -43 to 201132655 6 substituted with at least one fluorine atom; An alkyl group having a shape or a branch shape, an alicyclic hydrocarbon group having a carbon number of 4 to 10, which is substituted with at least one fluorine atom, or a group derived therefrom. Specifically, the structure represented by the following formula (2-2b) in the formula (2-2) is, for example, a structure represented by the following formulas (8-1) to (8-5). Among these, the structure represented by the following formula (8-5) is preferable. [化1 9] R10 - C - (2-2b) R10 [Chemical 2 0]

Η——c——F (8- ΗIC-cf(8-2

F-C-F -3) (8-

F-CICF3I rrCFa (8-5) The ratio of the repeating unit (2-2), when the total repeating unit of the (C) polymer is 100 mol%, preferably 80 mol% or less, and 20 ~80% by mole is better, with 30~70% by mole. When the content ratio is within the above range, there is an advantage in that the formed resist film can reduce the difference between the contact angle and the receding contact angle before the immersion exposure liquid. [1-3_3] The repeating unit represented by the formula (2-3): a divalent bond group represented by R7 in the formula (2-3), for example, a carbon-44-201132655 number of 1 to 30 The hydrocarbon base of the valence. In another example, the chain structure R7 obtained by combining the hydrocarbyl group, the imido group, the carbonyl '-C0-0- or -CO-NH- group, for example, has methane, ethane butane, 2-methyl group. a carbon number of 1 to 1 such as propane, pentane, 2-methylbutane, 2,2-di, hexane, heptane, octane, decane or decane. Hydrocarbyl group and the like. Further, R7 of the cyclic structure has, for example, cyclobutane, cyclohexane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]cyclo[5.2.1.02,6]nonane, tricyclo[3.3 .1.13,7] 20 alicyclic hydrocarbons such as decane are removed by the removal of two hydrogen atoms. The valence of the structure is such that two or more aromatic hydrocarbons having a carbon number of from 6 to 30 such as benzene or naphthalene are removed. . The carbon number represented by the RIQ in the formula (2-3) is 1 to 10 groups, and for example, at least one or more of the carbon atoms which are substituted with at least one or more fluorine atoms and which have a linear or branched alkyl group. The alicyclic hydrocarbon group having a carbon number of 4 to 10 or the R 8 of the general formula (2.3), specifically, for example, the following 3al) to (2-3a3) The base of the representation. Further, in the formula (: (2-3a2), 'R2 5 represents a halogen atom, an oxy 'indenyl group having a carbon number of 1 to 1 fluorene, or a decyloxy group, and R25 in which a plurality of R25 is present may be the same or different. Mi is an integer of 〇~5, an integer of 4~4. In the formula (2_3a3), each of R26 and R27 has a hydrogen atom or an alkyl group having a carbon number of 1 to 10, and R26 and R27 may each have a sulfur atom structure or the like. , a propane, a chain hydrocarbon of methyl propane, a cyclopentane octane, a hydrocarbon group having a carbon number of 4 to 4; a fluorinated alkane of a hydrogen atom; a substituent of a group of 1 to 6; 2-3al) and. In the case of the hospital base and the hospital, each * m 2 table does not stand alone: the bond formation -45- 201132655 carbon number 4~20 alicyclic structure. [Chem. 2 1]

CH-R26 I R27 (2-3a3) An atom represented by R25 in the formula (2-3a2), a chlorine atom, a bromine atom, an iodine atom or the like. This sub is preferred. The {, alkoxy group, fluorenyl group, decyloxy group represented by R25 in the formula (2-3a2), specifically, an oxime group or the like. The alkyl group represented by R26 or R27 in the formula (2-3a3), for example, a methyl group, an ethyl group, an η-propyl group or the like. Further, an alicyclic structure of a cyclopentylmethyl group, a 1-(1-cyclopentylethyl) group, a halogen atom, such as R26 and R27 which are bonded to each other in the formula (2-3a3), for example, Among the fluorines, the alkyl group having a fluorine atom number of 1 to 10, such as a methyl group, a methoxy group, and a carbon number of 1 to 10, is bonded to each other, for example, a cyclopentyl group 'h ( 2-cyclopentylethyl-46 - 201132655 ), cyclohexyl, cyclohexylmethyl, 1-(1-cyclohexylethyl), 1-(2-cyclohexylethyl), cycloheptyl, ring Heptylmethyl, 1-(1-cycloheptylethyl), 1-(2-cycloheptylethyl), 2-oritalyl, and the like. a group represented by the formula (2-3 a3 ), specifically, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 1-pentyl, 2 -pentyl, 3-pentyl, 1-(2-methylbutyl), 1-(3-methylbutyl), 2-(3-methylbutyl), neopentyl, 1 -hexyl, 2-hexyl, 3-hexyl, 1-(2-methylpentyl), 1-(3-methylpentyl), 1-(4-methylpentyl), 2-( 3-methylpentyl), 2-(4-methylpentyl), 3-(2-methylpentyl) and the like. Among these, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl and 2-butyl are preferred. The repeating unit (2-3), specifically, for example, a unit represented by the following formula (2-3-1). [Chem. 2 4] R1

F (2-3-1) (In the formula (2-3-1), R1 represents a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; R7 represents a divalent bond group; and R8 represents a hydrogen atom or an acid; Dissociable group, or base dissociative group). A compound which forms a repeating unit represented by the formula (2-3-1), for example, -47-201132655 ', a compound represented by the following formula (2-3-la) to (2-3-ld), and the like. Further, 'in the formula (2-3-la)~(2-3-ld)', R1 represents a hydrogen atom, a lower-grade courtyard group, or a lower-grade courtyard group, and R8 represents a hydrogen atom, an acid-dissociable group, or a base. Dissociative group. [化2 5]

(2-3-1 a) (2-3-1 b) (2-3-1 c) (2-3-1 d) The above formula (2-3-la)~(2-3-ld) In the above formula, R8 is a compound which is an acid dissociable group or an alkali dissociable group, and, for example, a compound wherein Ri is a hydrogen atom or a derivative thereof can be synthesized as a raw material. For example, when R8 is a group represented by the above formula (2-3al) to (2-3a3), the compound 'for example, a compound represented by the following formula (9-1) can be used with any of the following compounds The compound represented by the formula (9·2) to (9-4) is reacted. -48- 201132655 【化2 6】

'R7-C-R28

\ II \R1. . (In the formula (9-1), R1 represents a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; and R7 represents a divalent bond group; and R1^ each independently represents a hydrogen atom, a fluorine atom, or a carbon number of 1~ A fluorinated alkyl group of 10. Further, in the case where all of R1CI is not a hydrogen atom, R28 represents a hydroxyl group or a halogen atom). [化 2 7]

(In the formula (9-2), R2 5 represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a decyl group, or a decyloxy group, and in the case where a plurality of R25 are present, each R25 may be the same or Any difference is possible. R29 represents a halogen atom. ml represents an integer of 0 to 5). [化2 8]

-49- 201132655 (In the formula (9-3), R2 5 represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a fluorenyl group or a decyloxy group, and a plurality of R25 are present, and each R25 It may be the same or different. R3Q represents a halogen atom, and m2 represents an integer of 0 to 4). [Chem. 2 9] HO—CH—R26 I (9-4) R27 (In the formula (9-4), R 2 6 and R 2 7 each independently represent an alkyl group having 1 to 1 carbon atom). The halogen atom represented by R29 in the formula (9-2) is preferably a chlorine atom. The halogen atom represented by R3Q in the formula (9-3) is preferably a boron atom. The alkyl group having 1 to 10 carbon atoms represented by R26 or R27 in the formula (9-4), for example, a methyl group, an ethyl group, an η-propyl group or the like. Further, in the case where R8 in the formula (2-3) is a group represented by the above formula (2-3al) to (2-3曰3), a compound having such a group, for example, The compound represented by the formula (10-1) can be obtained by reacting with a compound represented by the following formula (10-2). [Chemical 3 0] R10 HO—R7—/—C—OR8 (10-1) (In the formula (10-1), R7 represents a divalent bond group; r8 is a formula (-50-201132655 2- 3al) to (2-3a3), the rig independently represents a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having a carbon number of 1 to 10. Further, all of R10 are not hydrogen atoms) 1】

(In the formula (10-2), R1 represents a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; and R47 represents a hydroxyl group or a halogen atom). The ratio of the repeating unit (2-3) is, in the case where the total repeating unit of the (C) polymer is 10% by mole, preferably 50% by mole or less, and 5 to 30% by mole. More preferably, it is particularly good at 5 to 20% by mole. When the content ratio is within the above range, the formed photoresist film has an advantage of having a good balance between water repellency and affinity for the developer. Further, the '(C) polymer, as described above, is at least one selected from the group consisting of a repeating unit (2-1), a repeating unit (2-2), and a repeating unit (2-3). The repeating unit is preferably one, and may have any one of repeating units (2-1) to (2-3), or two or more types may be used, and it is preferable to have two or more types. It is better to repeat units (2_2) and repeat units (2-3). In the (C) polymer, when at least one of the repeating unit (2-2) and the repeating unit (2-3) has an alkali-dissociable group, (c) the affinity of the polymer to the developing solution can be improved. It is presumed that the result of the reaction of the (C) polymer and the developing solution in the developing step of the formation method of the resist pattern described later to produce the polar -51 · 201132655 group. Further, in the case where R8 in the general formulae (2-2) and (2-3) is a hydrogen atom, the repeating units (2 - 2 ) and (2 - 3 ) are units having a polar group of a hydroxyl group or a carboxyl group. Then, when the '(C) polymer contains these repeating units, the affinity of the polymer (C) to the developing solution can be improved in the developing step of the method for forming the photoresist pattern described later. [1-3-4] Repeating unit (i): (C) The polymer further has at least a group represented by the following formula (2-4) and a group represented by the following formula (2-5) The repeating unit of any one of the bases (other than the repeating unit represented by the above formula (2-3)) (hereinafter, also referred to as "repeating unit (i)") is preferable. When the repeating unit (i) is further provided, the solubility of the formed photoresist film to the developing solution can be improved. [Chemical 3 2] 1 NH I 1 S 0 I COOH R11 (2-4) (2-5) (In the formula (2-4), Rn represents a hydrocarbon group having 1 to 10 carbon atoms substituted by a fluorine atom) The hydrocarbon group having 1 to 10 carbon atoms which is substituted by a fluorine atom represented by R11 in the formula (2-4), and 1 or 2 or more hydrogen atoms in the hydrocarbon group having 1 to 10 carbon atoms are each a fluorine atom. When the group is substituted, it is not particularly limited to -52-201132655. For example, a trifluoromethyl group or the like is preferable. The main chain skeleton of the repeating unit (i) is not particularly limited, and for example, methacrylate, acrylate, trifluoroacrylate or the like is preferable. The repeating unit (i) is, for example, a repeating unit produced by a compound represented by the following formula (1 1 - 1 ), a repeating unit produced by a compound represented by the following formula (11-2), and the like. [化3 3] R1

Ο HN \ 〇=S==0 / R31

(11-2) (1M) (In the formulae (11-1) and (11_2), R1 represents a hydrogen atom, a lower alkyl group or a halogenated lower fluorenyl group; and R32 represents a single bond, or a carbon number of 1 to 2? a linear or branched or cyclic saturated or unsaturated hydrocarbon group of the formula 2. In the formula (11-1), 'R31 represents a hydrocarbon group having 1 to 1 carbon atom substituted by a fluorine atom, and t is 0. Or 1). a linear or branched or cyclic saturated or unsaturated hydrocarbon group represented by R32 represented by R32 in the formula (Π-1) and (h_2), for example, and a general formula (6) The organic base of the two valence represented by R2 in the middle is the same content. The hydrocarbon group having 1 to 10 carbon atoms which is replaced by a fluorine atom represented by x' (11-.) is 1 or 2 or more of the hydrocarbon group -53-201132655 having a carbon number of 1-4. When the hydrogen atom is replaced by a fluorine atom, it is not particularly limited. For example, a trifluoromethyl group or the like is preferable. Further, a repeating unit (a type may be used alone or two or more types may be used. The ratio of the unit (i) is preferably 50 mol% or less, and more preferably 5 to 30 mol%, as the total repeat unit of the (C) polymer is 100% by mole. When the content ratio is within the above range, the formed photoresist film has the advantage of obtaining a good balance between water repellency and affinity for the developer solution ^1 -3-5] Other repeating units (b): (C) Polymer, in addition to the above repeating units (2-1) to (2-3) and repeating units (i), may contain other repeating units (b) The other repeating unit (b) is, for example, each repeating unit represented by the above formula (2-1) to (2-5), etc. Further, the weight expressed by the formula (2-1) In the unit, the repeating unit represented by the following formula (12) is preferred. When the repeating unit represented by the following formula (12) is contained, the difference between the forward contact angle and the receding contact angle of the resist film can be reduced. Therefore, the scanning speed during the immersion exposure can be improved. -54- 201132655 [Chem. 3 4] R1

(In the formula (12), R1 represents a hydrogen atom, a lower alkyl group, or a halogenated lower-grade courtyard group; and R33 represents a linear or branched municipal group having a carbon number of 1 to 4. k represents an integer of 1 to 4) . a linear or branched hospital group having a carbon number of 丨 to 4 represented by R3 3 in the general formula (12), for example, methyl, ethyl, η-propyl, i-propyl, n-butyl , 2-methylpropyl, 1-methylpropyl, t-butyl, and the like. (C) Since the polymer contains a fluorine atom, even if (a) the polymer contains a fluorine atom, the ratio of the fluorine atom is larger than that of the (A) polymer. When the total amount of the (C) polymer is 100% by mass, the content of the fluorine atom is preferably 5% by mass or more, more preferably 5 to 50% by mass, and more preferably 5 to 40% by mass. (c) When the content ratio of the fluorine atom in the polymer is within the above range, the water repellency of the formed photoresist film can be improved, and when the immersion exposure is performed, the underlayer film is not formed separately. The advantages of water-based photoresist film. Further, when the content ratio is lower than that of the (A) polymer, (a) the oil repellency of the polymer and the (C) polymer may be somewhat reversed, and if the oil repellency is reversed to some extent, (C) The polymer will not tend to favor the surface layer of the photoresist film, and the effect of the present invention cannot be obtained. -55- 201132655 (c) The content of the polymer is preferably 〇·1 to 20 parts by mass, based on 100 parts by mass of the (A) polymer, more preferably 〇. 5~1 〇 by mass, to 1 ~5 parts by mass is especially good. When the content is within the above range, since (c) the polymer tends to be on the surface layer of the photoresist film, it has an effect of obtaining good water repellency. (C) The polystyrene-equivalent weight average molecular weight (Mw) of the gel permeation chromatography (GPC) method of the polymer, preferably from 1, 〇〇〇 50,000 to 50,000, preferably from 1,000 to 40,000, more preferably , 〇〇〇~3〇, 〇〇〇 is especially good. When the above Mw is less than 1, the photoresist film having a sufficient back-off contact angle cannot be obtained, and there is a concern that the use of the immersion-type exposure liquid is a cause. Further, when it exceeds 50,000, there is a fear that the visibility of the photoresist film is lowered. Further, the ratio (Mw/M η ) of the Mw of the (C) polymer to the number average molecular weight (?η) in terms of polystyrene by the GPC method is preferably 1 to 5, more preferably 1 to 4. Further, the (C) polymer is preferably the same as the (Α) polymer, such that the content of impurities such as halogen or metal is lower. The lower the content of these impurities, the higher the sensitivity, resolution, process stability, pattern shape, etc. of the photoresist film. (C) a polymer, for example, a hydrogen peroxide, a dialkyl peroxide or a dimercapto peroxide may be used as a monomer (polymerizable unsaturated monomer) used for forming each of the above repeating units. A radical polymerization initiator such as an azo compound is produced by, if necessary, polymerization in a suitable solvent in the presence of a chain shifting agent. The solvent used in the above polymerization is, for example, the same as the solvent used in the polymerization of (A) polymer at -56-201132655. Further, the reaction temperature in the polymerization ' is usually 40 to 150 ° C, and more preferably 50 to 120 ° C. The reaction time is usually from 1 to 48 hours, preferably from 1 to 24 hours. [1-4] Other components: The sensitive radiation linear resin composition of the present invention may further contain other components in addition to the (A) polymer, (B) the radiation-sensitive linear acid generator, and the (C) polymer. Other ingredients, such as acid diffusion control agents, solvents, lactone compounds, other additives (eg, alicyclic additives, surfactants, sensitizers, antihalation agents, adhesion aids, preservation stabilizers) Foaming agent, etc.). [1-4-1] Acid Diffusion Control Agent: An acid diffusion controlling agent, for example, a compound represented by the following formula (13) (hereinafter also referred to as "nitrogen-containing compound (I)"), a compound having two nitrogen atoms in the same molecule (hereinafter also referred to as "nitrogen-containing compound (II)"), and a compound having three or more nitrogen atoms (hereinafter, also referred to as "nitrogen-containing compound" III)", a guanamine-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, and the like. When these acid diffusion controlling agents are further contained, the loyalty of the shape or size of the pattern can be improved. -57- 201132655 【化3 5】 R34

I /\ (13) r35 R36 (In the formula (13), R34 to R36 represent a mutually independent hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group or an aralkyl group which may be substituted. Or acid dissociable group). The acid-dissociable group in the compound represented by the above formula (13) is, for example, a group represented by the formula (13-1). [Chem. 3 6]

R3eΓΓ - ο I OMNC 3· (In the formula (13-1), R37 to R39 represent a linear or branched alkyl group having a carbon number of 1 to 4 independently of each other, or a carbon number of 4 to 20 An alicyclic hydrocarbon group or a group derived from the same, or R38 and R39 bonded to each other and simultaneously forming a carbon number of 4 to 20 alicyclic alicyclic hydrocarbon groups or a plurality of carbon atoms bonded thereto The derivatized group 'R37' represents a linear or branched alkyl group having 1 to 4 carbon atoms, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom. a linear or branched alkyl group having a carbon number of 1 to 4 represented by R3 7 to R3 9 in the formula (13-1), for example, a methyl group, an ethyl group, an η-propyl group, an i-propyl group , η-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, and the like. The alicyclic hydrocarbon group having a carbon number of 4 to 20, represented by R37 to R39 in the formula (13-1), for example, norbornane, tricyclodecane, tetracyclododeca-58-201132655 alkane, Adamantane, or a group formed of an alicyclic ring derived from a cycloalkane or the like, such as cyclobutane, cyclopentane, cyclohexane, cycloheptane or cyclooctane. R38 and R39 in the formula (13.1) are bonded to each other and form a divalent alicyclic hydrocarbon group having a carbon number of 4 to 20 at the same time as the carbon atom bonded to each other or a group derived therefrom. The divalent alicyclic hydrocarbon group is, for example, methyl, ethyl, η·propyl, i-propyl, η-butyl, 2-methylpropyl, hydrazine methylpropyl, t-butyl One or more or more substituted alkyl groups having a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms. In the nitrogen-containing compound (I), a compound having no acid-dissociable group, specifically, a tri-amine such as tris-n-hexylamine, tri-n-heptylamine or tri-n-octylamine. a compound having an acid dissociable group in the nitrogen-containing compound (I), specifically, g, for example, Nt-butoxymethyl-4_ylpiperidine, Nt-butoxypyridylpyrene, Nt-butoxyxanthene Dicyclohexylamine and the like. The nitrogen-containing compound (II) 'specifically, for example, n, n, n, n, -tetrakis(2-hydroxypropyl)ethylenediamine or the like. The nitrogen-containing compound (III) 'specifically, for example, a polymer of polyvinylimine, polydecylamine, monomethylaminoethyl decylamine or the like. A nitrogen-containing heterocyclic compound, for example, 2-phenylbenzimidazole, N-t-butoxycarbonyl-2-phenylbenzimidazole, or the like. Further, as the acid diffusion controlling agent, a compound represented by the following formula (丨4) can be used. X+Z- . . . (14) (In addition, in the above formula (14), 'χ+ is a cation represented by the following formula (or (-59-201132655 14-2). Z_ is OH· , an anion represented by R41-COCT of the formula (14-3), an anion represented by the formula (14-4) R4Q-S〇r, or a formula (14-5) R4()-N\S02-R41 Further, in the above formula (14-3) to (14-5), 'R4Q is an alkyl group, an alicyclic hydrocarbon group or an aryl group which may be substituted. R41 represents a fluorinated alkyl group which may be substituted. , alicyclic fluorinated hydrocarbon group or fluorinated aryl group) ° [Chem. 3 7]

In the above formula (14-1), R42 to R4 4 represent mutually independent hydrogen atoms, alkyl groups, alkoxy groups, hydroxyl groups, or halogen atoms, and in the above formula (14-2), R45 and R46 are independent of each other. A hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or a halogen atom. The compound represented by the above formula (14) can be used as an acid diffusion controlling agent (hereinafter also referred to as "photodecomposable acid diffusion controlling agent") which decomposes by exposure and loses acid diffusion controllability. Further, when the compound represented by the formula (14) is contained, the acid diffuses to the exposed portion, and when the acid diffuses to the unexposed portion, it is controlled, and the exposed portion and the unexposed portion are excellently contrasted (that is, the exposed portion) It is more clear with the boundary portion of the unexposed portion), in particular, the LWR, MEEF (Mask Error Enhancement Factor) can be effectively improved by using the sensitive radiation linear resin composition of the present invention (Mask Error Width -60-201132655 The widening factor of the line width offset)). X+ in the formula (14) is a cation represented by the above formula (Μ-ΐ) or (14-2) as described above. Further, R42 to R44 in the formula (14-1) represent mutually independent hydrogen atoms, alkyl groups, alkoxy groups, hydroxyl groups, or halogen atoms, among which compounds represented by the above formula (14) The effect of reducing the solubility in the developer is preferably a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. Further, R45 and R40 in the formula (14-2) represent a mutually independent hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or a halogen atom, and among them, a hydrogen atom, an alkyl group or a halogen atom is used. good. In the formula (14), an anion represented by the formula (14-3) R4 <)-COO·, an anion represented by the formula (14-4) R4G-S ΟΓ, or an anion An anion represented by the formula (14-5) R4Q-N, S02-R41 (also 'in the above formula (14-3) to (14-5), 'R4° is an alkyl group which may be substituted, an alicyclic hydrocarbon group Or aryl. R41 is a fluorinated alkyl group, an alicyclic fluorinated hydrocarbon group or a fluorinated aryl group which may be substituted. Among the acid diffusion controlling agents, a nitrogen-containing compound (1), a nitrogen-containing compound (II), and a nitrogen-containing heterocyclic compound 'photodegradable acid diffusion controlling agent' are preferred. Further, the acid diffusion controlling agent may be used singly or in combination of two or more. The content of the acid diffusion controlling agent is preferably 1 part by mass or less based on 100 parts by mass of the (A) polymer, and more preferably 5 parts by mass or less. When the content of the acid diffusion controlling agent exceeds 10 parts by mass, there is a fear that the sensitivity of the formed photoresist film is remarkably lowered. -61 - 201132655 [1-4-2] Solvent: Solvent, for example, linear or branched ketone; cyclic ketone; propylene glycol monoalkyl ether acetate; 2-hydroxypropionic acid alkyl ester ; 3-alkoxypropionic acid alkyl esters and the like. These solvents may be used alone or in combination of two or more. Among them, linear or branched ketones, cyclic ketones, and propylene glycol monoalkyl ether acetates may be used. Further, an alkyl 2-hydroxypropionate or an alkyl 3-alkoxypropionate is preferred. [1-4-3] Lactone compound: A lactone compound is a compound which can effectively bias the (C) polymer to the surface layer of the photoresist film. That is, as a result of containing the lactone compound, the amount of the (C) polymer added in order to cause water repellency in the surface layer of the photoresist film during immersion exposure can maintain the photoresist film in a smaller amount than in the prior art. Water repellency of the surface layer. Further, in addition to the basic characteristics such as LWR, development defects, and pattern collapse resistance, it is also possible to control the components ((B) acid generator, etc.) in the photoresist film to be dissolved in the immersion exposure liquid. In the case of high-speed immersion exposure, droplets are not easily deposited on the photoresist film, so that a photoresist film can be formed under the defects caused by the immersion exposure liquid such as water spot defects. A lactone compound, for example, 7-butyrolactone, valerolactone, mevalonic lactone, ornidyl lactone, and the like. Further, the lactone compound may be used alone or in combination of two or more. The amount of the lactone compound to be used is preferably from 30 to 200 parts by mass, more preferably from 50 to 150 parts by mass, per 100 parts by mass of the (A) polymer. When the amount used is within the above range, the (C) polymer may be biased toward the surface of the photoresist film even when the amount of the (C) polymer used is small. When the amount of use of the above (C) polymer is less than 30 parts by mass, there is a concern that the surface of the photoresist film is not sufficiently water-repellent. On the other hand, when it exceeds 200 parts by mass, the basic properties and shape of the formed photoresist film may be remarkably deteriorated. The sensitive radiation linear resin composition of the present invention can be, for example, a mixture of (A) polymer, (B) radiation sensitive linear acid generator, (C) polymer, and other components (excluding solvents), and is fully solid-shaped. The composition is dissolved in a solvent in a concentration of 1 to 50% by mass (preferably 1 to 25% by mass), and then a composition solution is prepared by, for example, filtration using a filter having a pore diameter of about 0.2 m. [2] Method for forming photoresist pattern: The method for forming a photoresist pattern of the present invention comprises forming a photoresist film having a photosensitive resin composition of the present invention coated on a substrate to form a photoresist film. a step of exposing the immersion-type exposure liquid to the formed photoresist film, irradiating the photoresist film with radiation by the immersion-type exposure liquid, and using the developer solution to irradiate the photoresist film A method of developing to form a development step of a photoresist pattern. According to these methods, a photoresist pattern having a good LWR and having a lower film reduction can be formed. -63-201132655 [2-1] Photoresist film formation step: The photoresist film formation step is to be sensitive to the present invention. The step of linearly coating the radiation on the substrate to form a photoresist film. A substrate, for example, a germanium wafer, an aluminum-coated wafer, or the like. A method of forming a photoresist film on a substrate, for example, a method of dissolving a composition obtained by dissolving a radiation composition in a solvent, a conventionally known method such as a coating method, a roll coating method, or the like. The thickness of the photoresist film is not particularly limited, and the known photoresist film has the same thickness. Further, after the formation of the photoresist film, the photoresist film can be heated by "PB". [2 - 2] Exposure step: The exposure step is such that a immersion liquid is disposed on the formed photoresist film and irradiated with radiation through the immersion exposure liquid. The immersion exposure liquid, for example, pure water or radiation used for fluorine-based immersion exposure, may be appropriately selected in accordance with the type of the generating agent, for example, visible light, far ultraviolet ray, X-ray, charged electron beam, etc. Among them, the far-ultraviolet light represented by the molecular laser (wavelength 193 nm) or the KrF excimer laser ( ) is preferable, especially the sensitive radiation solution of the ArF quasi-resin composition, which is applied to the substrate by spin coating. It is the same as the conventional treatment (the following stepping liquid for the photoresist for the exposure type exposure, etc.. The acid line and ultraviolet light used are more preferably ArF quasi-wavelength 248 nm sub-laser (wave-64-201132655 length 193 nm). The exposure conditions such as the amount can be appropriately selected in accordance with the addition composition of the photoresist composition or the type of the additive, etc. Further, after the exposure, the heat treatment is further performed (heat treatment after the exposure, which is also referred to as "PEB" hereinafter. In the case of PEB, the dissociation reaction of the acid dissociable group in the (A) polymer can be carried out more smoothly. The heating condition of the PEB is the composition of the photoresist composition. The change is usually 30 to 200 ° C and 50 to 170 ° C. It is also used to derive the maximum potential of the sensitive linear resin composition, so it can be pre-formed before the photoresist film is formed. An organic or inorganic anti-reflection film is formed on the surface (for example, Japanese Patent Publication No. Hei 6-1-2942, etc.). A protective film can also be formed on the photoresist film by the influence of an impurity or the like (for example, JP-A No. 5-8 8 8 9 8 or the like). Further, the sensitive radiation linear resin composition of the present invention does not require formation of an infiltrating upper layer. The film may be formed by a user, that is, a composition of a photoresist film which has a good LWR after development and which is less likely to cause film reduction. For example, it is possible to form an infiltrated upper layer as disclosed in Japanese Laid-Open Patent Publication No. 2005-3 523 84 Further, the techniques may be employed. [2-3] Developing step: The developing step is a step of developing a photoresist film obtained by irradiation with radiation in a developing solution to form a photoresist pattern. a developing solution used for development, for example, dissolved in sodium hydroxide, hydrogen and oxygen Potassium, sodium carbonate, sodium citrate, sodium methyl citrate, ammonia, ethylamine, η-propyl-65- 201132655 amine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, Ethyl dimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-di It is preferred to obtain at least one of the obtained basic aqueous solutions of a basic compound such as azabicyclo-[4.3.0]-5-decene. The concentration of the basic aqueous solution is usually 10% by mass or less. When the concentration of the aqueous solution exceeds 1% by mass, there is a concern that the non-exposed portion is also dissolved in the developer. An organic solvent may be further added to the developer formed by the above aqueous alkaline solution. An organic solvent such as acetone, methyl ethyl ketone, methyl i-butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, 2,6-dimethylcyclohexanone or the like Class; methyl alcohol, ethyl alcohol, η-propyl alcohol, i-propyl alcohol, η-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol And alcohols such as 1,4·hexane dihydroxymethyl ester; ethers such as tetrahydrofuran and dioxane; esters of ethyl acetate, η-butyl acetate, i-amyl acetate, etc.; toluene, xylene, etc. Aromatic hydrocarbons, or phenol, acetone acetone, dimethylformamide, and the like. These organic solvents may be used singly or in combination of two or more. The amount of the organic solvent to be added is preferably 1% by volume or less based on the aqueous alkaline solution. When the amount of the organic solvent added exceeds 1% by volume, the developability is lowered, and there is a fear that a plurality of development residues may remain in the exposed portion. Further, an appropriate amount of a surfactant or the like may be added to the developer formed by the aqueous alkaline solution. Further, after development of the developer formed by the aqueous alkali solution, it is usually washed with water and dried. [Embodiment] -66 - 201132655 [Examples] Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited by the examples and comparative examples. In addition, the conditions described in "parts" and "%" refer to the quality standard unless otherwise stated. Further, the measurement methods of various physical properties and the evaluation methods of various characteristics are as follows. [Dissolution amount]: Using a CLEAN TRACK ACT8 (manufactured by Tokyo Electronics Co., Ltd.), a radiation-sensitive linear resin composition (a composition solution) was spin-coated on a tantalum wafer, and baked at 100 ° C for 60 seconds. A tantalum wafer having a photoresist film having a film thickness of 150 nm was formed. A Teflon "ring" having a diameter of 1 cm and a thickness of 1 mm was placed on the silicon wafer to fill the ultrapure water lm L so that the ultrapure water was in contact with the photoresist film. After the ultrapure water and the photoresist film are respectively contacted for 3 seconds, 5 seconds, 10 seconds, 30 seconds, 60 seconds, 120 seconds, and 300 seconds, the glass syringe is used to recover the excess. Pure water is used as a sample for analysis. Further, the recovery rate of the ultrapure water after the end of the experiment was over 95%. Next, the column used for measuring the peak intensity of the anion portion of the photoacid generator in the ultrapure water was "CAPCELL PAK MG" manufactured by Shiseido Co., Ltd., using a tube of 0.2 ml/min, and measuring temperature 3 5 °C, a solution obtained by adding 0.1% by mass of formic acid to water/methanol (3/7) as an effluent solvent, LC-MS (Liquid chromatography analysis, LC: SERIES 1100, MS manufactured by AGILENT) Department: -67- 201132655

Measurement was carried out by Mariner (manufactured by Perseptive Biosystems, Inc.). At this time, 'the peak intensity of each of the lppb, lOppb, and 100 ppb aqueous solutions of the photoacid generator' was prepared, and the calibration curve measured by the above measurement conditions was used, and the calibration curve was used. The amount of elution was calculated from the above peak intensity. The evaluation criteria is that the case where the elution amount is 2·0Χ10'12mol/cm2/sec or more is "poor", and it is less than 2 _ 0 X 1 (Γ 12m / cm 2 / sec is "good". [Sensitivity]: A 12-inch wafer having an anti-reflection film ("ARC66", manufactured by Nissan Chemical Co., Ltd.) having a thickness of 10 nm was prepared, and the composition solution was spin-coated on the surface of the wafer. The method is applied to a film of a substrate, and is subjected to light baking (SB; Soft Bake) on a hot plate at a temperature (10 ° C) shown in Table 5 (in Table 5, simply referred to as " SB") to form a photoresist film having a film thickness of 90 nm. On the photoresist film having a film thickness of 90 nm formed, Ricoh's all-round reduction projection immersion exposure apparatus ^ S610C j (number of openings 1.30) The mask pattern was exposed. Thereafter, PEB (PEB) was applied at a temperature of Table 5 for 60 seconds, and then developed in a 2.38 mass% TMAH aqueous solution at 25 ° C for 30 seconds, washed with water, and dried to form a pattern. Positive resistive pattern. At this time, the line width formed by a mask of 1 to 1 line and space of 45 nm is formed to form a line width of 45 nm. 1 Line and space exposure amount (mJ/cm2) as the optimum exposure amount' The optimum exposure amount (mJ/cm2) is used as the "sensitivity". -68- 201132655 [LWR (Line Width Roughness)]: Use the above [ The optimum exposure amount estimated in Sensitivity] forms a 45nm (1L/1S) pattern on the photoresist film, and the 45nm (1 L/1 S) pattern formed will use the length measurement SEM (Hitachi Hi-Tech) The company model, model "CG4000") is observed from the upper part of the pattern, and the line width is measured at any point. The measurement parameters obtained by measuring the line width are expressed as 3 ,, and the LWR is evaluated by the number. [Top consumption]: The observation of the 45nml L/lS pattern obtained by the best exposure amount is used to observe the cross section of the pattern using a scanning electron microscope (SEM) "S-4800" manufactured by Hitachi High-Tech Co., Ltd. The height (pattern height) was measured. Then, the top consumption was calculated from the difference between the height of the pattern and the initial film thickness (9 Onm) and the top consumption was evaluated by the top consumption. In 12, the combination represented by the following formula (M-1) to (M-1 5 ) is used. Each of the polymers (A-1) to (A-8) ((A) polymer) was produced. -69- 201132655 [Chemical 4 0]

-70-201132655 (Synthesis Example 1) (Production of polymer (Al)) Compound (m-ι) represented by formula (M-1): 24.61 g (30 mol%), formula (M-8) The compound (m-8) represented by 54.19 g (50 mol%), and the compound represented by the following formula (M-9) (M-9) 9.08 g (10 mol%) dissolved in 2-butanone 2 In 〇〇g, 4.00 g of dimethyl 2'2'-azobisisobutyronitrile was further added thereto to prepare a monomer solution. In addition, a mixture of 12.11 g of compound (μ-5) represented by formula (M-5) and 100 g of 2-butanone of l-butanol in a three-necked flask was blown with nitrogen for 30 minutes. The reaction vessel was heated to 80 ° C with stirring, and the above monomer solution was prepared by dropwise addition using a dropping funnel over a period of 3 hours. The polymerization reaction was carried out for 6 hours using the dropping start time as the polymerization starting time. After the completion of the polymerization, the polymerization solution was cooled to 3 liters or less by water cooling. Thereafter, it was poured into 2000 g of methanol to precipitate a white powder, and the precipitated white powder was filtered off. The white powder which was filtered off was washed twice with a slurry of 40 g of methanol, followed by 'filtering out and drying at 50 ° C for 17 hours* to obtain a white powder of a copolymer (yield 79 g, yield) 79%). The copolymer had a Mw of 5,500, Mw/Mn = 1.41, and a C-NMR analysis result, as shown in Table 3, a compound (1) and a formula (M-5) represented by the formula (Μ-1). The content of each repeating unit produced by the compound (M-5), the compound (M-8) represented by the formula (M-8), and the compound (m-9) represented by the formula (M-9) ( Moer %) is 30.2 : 9.9: 10_2: 49.7. This copolymer was used as the polymer (A-1). Further, the physical properties of the polymer (A-1) are shown in Table 3. -71 - 201132655 (Synthesis Examples 2 to 8) (Production of Polymers (A-2) to (A-8)) Except for the compounds (monomer types) and addition ratios shown in Table 1, all were synthesized according to the synthesis examples. The polymer (A-2) to (A-8) was produced in the same manner. Further, the physical properties of the polymers (A-2) to (A-8) are shown in Table 3. -72- 201132655 [1® Other monomer addition rate (mol%) 1 II 1 1 I o I Monomer type 1 II 1 1 I M-10 I mm * Addition rate 莫 (mol %) S 8 S 1 σ> CO o 扣 扣 扣 1 monomer type M-8 M-8 M-8 M-8 1 M-8 M-8 M-8 specific monomer addition rate indifference %) 〇〇 aso III M-9 M-9 cn 士 M-9 M-9 III Monomer addition rate of acid-dissociable group (% by mole) 1 II 1 1 II o Monomer type 1 II 1 1 II M-5 Addition rate ( Moer %) 〇〇I 1 1 CO 〇o monomer type M-5 M-5 I 1 1 M-4 M-5 M-4 Addition rate 莫 (mole%) 8 gggg in ·»— oo monomer Species M-1 M-1 1 Έ M-6 M-1 CsJ Έ M-1 j S Polymer < A-2 A-3 I A-4 A~5 A-6 A-7 A-8 -73 - 201132655 (Synthesis (polymerization to ear %) Mohr % 1 9.06g base 2,2 1 000m Nitrogen blowing the above single row 6 small cooling to thereafter, alcohol, monomethyl group, the yield is expressed as the knot of M -1 3 ) (MP (Production of Molybdenum (Example 9) (C-1)) Compound (m-3) represented by formula (M-3) 50.88 g (60 mol, formula (m-13) ) Compound (μ·13) 3〇.〇 6g (i5 ')' and the compound (m-14) (25 mol%) represented by the formula (M-14) are dissolved in 2 -butanone 1 〇〇g, and then added to dimethyl '-azobisisobutylene Nitrile 3.55 g to prepare a monomer solution. In addition, l〇〇g of 2-butanone was added to a three-necked flask, and after 30 minutes of incorporation, the reactor was heated to 8 Torr with stirring; The second 'use the dropping funnel' was dropped into the body solution prepared in advance for 3 hours. The polymerization start time was used as the polymerization start time, and the polymerization reaction was carried out. After the completion of the polymerization, the polymerization solution was cooled to 3 ° C or less by water cooling. 'The polymerization solution was transferred to a 2 L separatory funnel. The polymerization solution was diluted with 300 g of η-hexane, mixed in a row of i2 〇〇g, and allowed to stand for 30 minutes, and the lower layer was recovered as propylene glycol ether acetate. Solution: 65% of the solid content (polymer) of the propylene glycol monomethyl ether acetate solution, Mw was 6400, Mw/Mn was 1.41, 13C-NMR was determined, and the fluorine content was found to be 9 · 14% by mass. a compound of the formula (M-3), a compound (M-13) represented by (M-3), a compound represented by the formula (M-13), and a formula (M) -14) The content rate of each repeating unit produced by the compound represented by the compound is 60.3: 24.9: 14.8. The copolymer was prepared as the same method as in Synthesis Example 9 except that the compound (monomer type) and the compounding ratio shown in Table 2 were used, except that the compound (monomer type: 〇~1 2 ) was used. Polymer (C-2) ~ (C-4). Further, the physical properties of the polymers (C - 2 ) to (C - 4 ) are shown in Table 3. [Table 2] Polymeric acid-dispersing group-containing monomer Fluoride-containing monomer monomer type addition ratio (mol%) Monomer·addition rate (mol%) Monomer·addition rate (mol%) C -1 M-3 60 M-13 25 M-14 15 C-2 M-7 60 M-13 25 M-14 15 C-3 M-2 70 M-12 30 One — C-4 M-7 40 M -15 60 一 - -75- 201132655 4j ^ 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 9.13 9.30 10.20 9.03 φι C Έ \ 1.41 1.43 1.39 1.48 1.39 1.38 1.39 1.41 1.38 1.41 1.45 Έ 5 ο ο 5500 Ο Ο 5500 Ο ο 6400 ο ο ο Έ ΙΛ ιη CO g σ> (Ο 00 ιη eg ιη σ) ιη Ο C0 CO S ΙΟ ΙΟ 1 | II ο 卜 | 1 I 1 异 1 1 II ο σ > CO 1 1 1 1 m “ήτΐ! m CD CO I 1 1 I ο CO II 1 I Turn GQIQ Έ Έ Έ 酹 content ratio (% by mass) 10.2 10.2 19.7 20.5 I 39.7 40.4 10.8 14.8 "Τ* 1 1 m *r\ r\ <tm11 m σ&gt ; σ) CO cp 1 CO CO LO Τ quot quot 听 听 听 听 听 § § § σ 酹 冢 § § σ gt gt 10.C 19.£ 20.Ε 39j 45.Ϊ ιη ai CO σΐ 24.£ 25.: 30.1 59.ί m <Kf\ limit Delete gif ιη ιη 05 ? σ> 下ιη τΤ r* Έ Έ Έ Έ Έ Έ Έ 2 Έ Έ Έ ss w 30.2 49.3 60.5 58.9 60.3 14.6 40.1 39.9 60.3 59.6 69.9 40.5 & •F!^\ «Imll m III CD 1 CSi Τ Ι 1·* I C0 rp Cjsl Γρ Έ Έ Έ 2 Έ Έ Έ Έ 酹 酹 Polymer < Α-2 Α-3 Α-4 Α-5 (Ο < Α-7 Α-8 ύ CSi Ο C-3 Ο -76- 201132655 Next 'Example and The "acid generator" and the "acid diffusion control agent" used in the comparative examples are as follows. [化4 1]

F2 f2 F3C〆, 〆, so3 F2 (B-1)

(B-5) -77- 201132655 [Chem. 4 2]

(Ο-D

(0-2)

(D-5)

Further, the "solvent" and "additive" used in the examples and comparative examples are as follows. Solvent (E-1): propylene glycol monomethyl ether acetate, solvent (E-2): cyclohexanone, additive (F-1): r - butyrolactone. (Example 1) 100 parts of the polymer (-78-201132655 Al) produced in Synthesis Example 1 as a polymer (A), and the above formula (B-丨) as a (B) acid generator Compound (B-1) 1 part, 2 parts of polymer (C-1) produced according to Synthesis Example 9 as (c) polymer, and represented by the above formula (D-1) as an acid diffusion controlling agent 1.2 parts of the compound (d-1), 1 800 parts of a solvent (E-1) as a solvent, 75 parts of a solvent (E_2), and 30 parts of an additive (F-1) as an additive to prepare a sensitive substance A composition solution obtained by irradiating a linear resin composition. Subsequently, the above various evaluations were carried out using the obtained composition solution. In the sensitive radiation linear resin composition of this example, the evaluation of the dissolution amount was "good" and the sensitivity was 20.0 mJ/cm2, and the evaluation of the LWR was 3.5 rim, and the evaluation of the top consumption was I5nm. (Examples 2 to 18, Comparative Examples 1 to 4) A composition solution composed of each of the radiation sensitive linear resin compositions was produced in the same manner as in Example 1 except that the compound shown in Table 4 and the amount of addition were used. The above various evaluations were carried out using the respective composition solutions prepared. The evaluation results are shown in Table 5. -79 - 201132655 □ 1 _甶后ΙΜ Tengyi 8 Another O CO o co O o 8 o C9 o CO 〇CO Μ WS ilflUj m lL 丄I r* Ll t·· 丄丄丄丄r· ll· 丄丄丄lL 1— 丄I ί iL U- ▼·· 丄iL Y— 丄▼*· 丄T— 丄1 t-· 丄蘅m 君 _ s Ρ-» g r- gg 卜 r- o in SS Ο ΙΟ o in s ο LO o in o in ssss r- s 卜 S 卜 o JO o JO o Ln ο jn s & ilrfTlI m Csl LU CM mountain CM mountain eg mountain eg Ui CSI mountain eg mountain eg LU CJ4 mountain Cjsl UJ Cs( LU CNJ LU Csl LU C*J LU csi m Csl UJ CNJ LU CM LU CNJ UJ OJ 111 CNJ mountain cjg mountain CSI mountain OJ mountain eg mountain _ 裘君 _ 〇〇〇 1 1 o 00 O 00 o 00 Ο CO | | oc〇〇00 o 00 oso 00 〇CO | Ο 00 o 00 o 00 o 00 〇00 ο 00 Shock • Kr» t»wi1 m I Σ ll I 1 Σ 1 Σ Σ lll Σ lll LU Τ » LU ll Σ 蘅Μ 雔饀 _ _ « Ι Ι CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN CN C>J CNJ Csl CNJ m P τ α Ύ— Ο QQ o 〇TQ τ~· QQT~ Q Cjs l Q cp QY a vn 〇CO QQQ a Ω Q r— Q τ α Q § <Π ϋ ϋ _ csl CM in CM eg Csl CM eg CM CVJ CM CM CM m Cvj ιο 04 m oi CNJ m in ΙΟ 1 m iimn 郷y^~ 6 CNJ Ο cp 〇 〇» 〇1 〇ό ύ 〇ύ 1 〇1 o 1 〇1 〇cp 〇CO 〇CO 〇〇CO 0 CO 〇CO ό 1 11 S _φ 吕¢ 1 滕麫〇o ο ο oo O o' in (〇σ>σ> 00 CD σί c\io o' O o 〇〇O ood (O CO CO o' (O csi CO csi 〇o' 〇doo ο ο 〇〇m “mil P S"· 1 CQ ι 1 m r-» CQ CNI m ? QQ ω in 00 CO CO »·» ffl T CO CD T ω T ω in m CO GD CO m CO CO T CD T CD r" ffl CQ CD <〇龄_φ后_腾® o Ο O 〇oooo ο Ο 〇o 〇oo O o O o O ssoooo ο ο 〇mw < ^-* < 1 < 1 < t << 1 < 1 <<<<< 1 - < eja < ? < cp << in < CO < r- < CO < 1 &lt i grip w CM reveal in CO 匡m 刺 inch grip w in 匡m flu; (0 揭κ i grip ship 00 mmw 0) m K 0 1 闺« i 闺CNJ i 揭 n CO i佩i 闺Im 10 5 mn (0 i 舾 II 00 i 闺K i 镒jj JA CNJ 镒ΛΑ C0 镒 inch aa -80- 201132655 [Table 5] SB (°C) PEB (°C) Dissolution amount sensitivity (mJ/cm2) LWR (nm) Top Consumption (nm) Example 1 100 95 Good 20.0 3.5 15 Example 2 100 95 Good 19.5 3.5 13 Example 3 100 95 Good 20.5 3.7 14 Example 4 100 95 Good 19.0 3.6 16 Example 5 100 95 Good 20.0 3.5 14 Example 6 100 95 Good 21.0 3.4 13 Example 7 100 95 Good 19.5 3.3 12 Example 8 100 95 Good 20.5 3.2 11 Example 9 100 95 Good 20.0 3.6 12 Example 1 〇100 95 good 20.0 3.2 14 Example 11 100 95 Good 22.0 3.1 11 Example 12 100 95 Good 21.0 3.2 12 Example 13 100 95 Good 20.5 3.1 11 Example 14 100 95 Good 19.0 3.1 11 Example 15 100 95 Good 20.0 2.8 15 Example 1 6 100 95 Good 19.5 3.0 16 Example 17 100 95 Good 19.0 2.9 17 Example 18 100 95 Good 17.0 4.1 14 Comparative Example 1 100 110 Good 22.5 3.7 24 Comparative Example 2 100 95 Good 23.0 3.6 29 Comparative Example 3 100 100 good 21.0 3.6 27 Comparative Example 4 100 - Poor - - - As can be seen from the contents of Table 5, the sensitive radiation linear resin compositions of Examples 1 to 18 were compared with the sensitive radiation linear resin compositions of Comparative Examples 1 to 4, It was confirmed that it had a good LWR after development, and it was not easy to cause film reduction. [Industrial Applicability] The sensitive radiation linear resin composition of the present invention is suitable as a semiconductor. -81 - 201132655 The photoresist used in the lithography technique in the field of manufacturing. The method for forming a photoresist pattern of the present invention is suitable as a method of forming a fine pattern in a lithography technique in the field of semiconductor fabrication. -82-

Claims (1)

201132655 VII. Patent application scope: 1 · A sensitive radiation linear resin composition characterized by containing (A) a repeating unit represented by the following general formula (1), and a polymer having an acid dissociable group, and B) a sensitive radiation linear acid generator, and (C) a polymer containing a fluorine atom, [Chemical 1] (In the formula (1), 'R1 represents a hydrogen atom' lower alkyl group, or a halogenated lower alkyl group; and R2 represents a single bond, a carbon number of 〜5, a divalent hydrocarbon group, an alkanediyloxy group or an alkanediyl group. Carbonyloxy; R3 represents a trivalent organic group). 2. The sensitive radiation linear resin composition of claim 1, wherein the repeating unit represented by the above formula (1) is a repeating unit represented by the following formula (!_:!), -83-201132655 [ 2] R50 (in the formula (1-1), R1 represents a hydrogen atom, a lower alkyl group, or a halogenated alkyl group; and R2 represents a single bond, a hydrocarbon group having a carbon number of 1 to 5, a oxy group, a oxy group, or an alkane a carbonyloxy group; r5 〇 represents a group represented by the following formula (a) or a group represented by the following formula (b): (In the formula (a), nl represents an integer of 0 to 2; in the formula (b), n5 each independently represents an integer of 〇~2; in the formula (a) and the formula "*" represents a formula (1) 1) a bonding bond with an R2 bond; and, in the group represented by (a) and the group represented by the formula (b), at least one of the carbon atoms constituting the group may be an oxygen atom or a nitrogen atom. Or a carbonyl group: Further, a group represented by the formula (a) and a group represented by the formula (b), and a substituent of the formula η 2 (b) may have a substituent of -84 to 201132655. 3. The radiation sensitive linear resin composition of claim 2, wherein the repeating unit represented by the above formula (1) is a repeating unit represented by the following formula (1_1a), [Chemical 4] (In the formula (Ι-la), R1 represents a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; R2 represents a single bond, a carbon number of 1 to 5 carbon atoms, an alkanediyloxy group or a a bis-carbonyloxy group; Rh represents a group represented by the following formula (al) or a group represented by the following formula (bl); (In the general formula (al) and the general formula (bl), * represents a bonding bond bonded to R2 in the general formula (i-ia)). 4. The sensitive radiation linear resin composition of claim 1, wherein the (C) polymer has each represented by the following general formula (2-1) to (2-85-201132655 3) Repeating at least one repeating unit selected by the group formed by the repeating unit, (In the formula (2-1) to (2-3), 'R1 represents a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group; in the formula (2-1), 'R9 represents a fluorine having a carbon number of 1 to 3 fluorene. In the formula (2-2), 'R6 represents a single bond or a (g+Ι) valence bond group, and g is an integer of 1 to 3: in the formula (2-3), R7 represents a divalent value. Bonding group: In the formula (2-2) and the formula (2-3), R8 represents a hydrogen atom, an acid dissociable group, or an alkali-dissociable group, and R1() each independently represents a hydrogen atom or a fluorine atom. Or a fluorinated alkyl group having a carbon number of 1 to 1 Å; and, in the case where all of R1() is not a hydrogen atom), the sensitive radiation linear resin composition of claim 4, wherein the above (C) a polymer having a repeating unit containing at least one of a group represented by the following formula (2_4) and a group represented by the following formula (2-5) (again, the above formula (2- 3) Except for the repeating unit indicated, -86- 201132655 [Chemical 7] 〇=S=〇1 COOH R11 (2-4) (2-5) 1~1 0 (In the formula (2-4), Ri丨 denotes a hydrocarbon group in which the sleeve gas mask is not replaced by a fluorine atom). 6. The sensible radiation linear resin composition of the fifth aspect of the patent scope of the invention, wherein the ruthenium of the Bn# (C) polymer is 0.1 to 40 parts by mass based on 1 part by mass of the polymer. 7. A method for forming a photoresist pattern, comprising: applying a radiation sensitive linear resin composition according to any one of claims 1-6 to a substrate to form a photoresist film; a photoresist film forming step of disposing a immersion-type exposure liquid on the formed photoresist film, irradiating the photoresist film with radiation by the immersion-type exposure liquid, and irradiating the radiation with a developing solution The latter photoresist film is then developed to form a photoresist pattern development step. -87- 201132655 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is a simple description: No-3-201132655 If there is a chemical formula in the case, please reveal the best invention Chemical formula of the feature: none