TW201013309A - Radiation-sensitive resin composition, method for forming resist pattern and photoresist film - Google Patents

Abstract

Disclosed is a radiation-sensitive resin composition which hardly dissolves into a liquid for immersion exposure with which the resin composition comes in contact during a liquid immersion exposure, and has a large receding contact angle with the liquid for immersion exposure. The radiation-sensitive resin composition can form a resist film which is capable of highly precisely forming a fine resist pattern having less development defects. The radiation-sensitive resin composition is used for formation of a resist film in a method for forming a resist pattern which comprises an immersion exposure step, and contains a resin component, an acid generator and a solvent. The resin component contains a resin (A1) which contains a repeating unit (a1) having a fluorine atom and an acid-cleavable group in a side chain. The resin composition is characterized in that the value of K1 defined by the following formula: K1 = F1/F2 (wherein F1 represents the fluorine content ratio in the outermost surface portion of the resist film, and F2 represents the fluorine content ratio in the portion from the outermost surface to the position around 20% of the thickness of the resist film) satisfies the following formula: 1 = K1 = 5.

Description

201013309 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 liquid for liquid immersion exposure, a polymer, and a photoresist pattern. More specifically, the present invention is suitable as various radiation lines such as X-rays, electron beams, and the like, which can be used for K-F excimer lasers, Far-ultraviolet light represented by ArF excimer lasers, synchrotron radiation, and the like. Liquid immersion used for microfabrication of chemically amplified photoresists. Method for forming a polymer and a photoresist pattern of a sensitive radiation linear resin composition for exposure. [Prior Art] In the field of microfabrication represented by the manufacture of integrated circuit components, in order to obtain a higher degree of integration, a microfabrication technique capable of finely processing at a level of 0.10 μm or less has recently been required. However, in the past lithography process, near-ultraviolet light such as radiation was generally used, but this near-ultraviolet light is generally considered to be extremely difficult to achieve micro-machining of the sub-fourth minute sub-micron level. Therefore, in order to be able to perform fine processing at a level below Ο.ΙΟμιη, it is possible to review radiation having a shorter wavelength. Such short-wavelength radiation, such as a bright line spectrum of a mercury lamp, a far-ultraviolet light represented by an excimer laser, an X-ray, an electron beam, etc., wherein a KrF laser (wavelength 248 nm), or an ArF excimer mine The shot (wavelength 193 nm) is attracting attention. Suitable for the resist of such excimer laser irradiation, there have been many reports of, for example, the use of components having an acid-dissociable functional group and irradiation of radiation (hereinafter referred to as "exposure") to produce an acid component (hereinafter referred to as A photoresist that produces a chemical amplification effect (hereinafter referred to as "chemically amplified photoresist") for "acid generation-5 - 201013309". From the viewpoint of the development of technology that can be used for the miniaturization of integrated circuit components, there is a strong need for radiation that can accommodate short wavelengths represented by far-ultraviolet light, high transparency to radiation, and sensitivity, resolution, and pattern shape ( Profile) A chemical 型-type photoresist that is excellent in basic physical properties such as photoresist. In the above lithography process, it is required to form a finer pattern (e.g., a fine photoresist pattern having a line width of about 90 nm). In order to achieve a finer pattern than this 90 nm, it is considered that the wavelength of the light source of the exposure apparatus as described above is shortened or the number of apertures (NA) of the lens is increased. However, the short wavelength of the wavelength of the light source requires a new exposure device, which increases the cost of the device. Further, since the high NA of the lens has a resolution and a depth of focus as a trade-off relationship, even if the resolution is improved, there is a problem that the depth of focus is lowered. In recent years, a lithography technique that can solve such a problem has a method of liquid immersion exposure (Liquid Immersion Lithography). The method is a liquid refractive index medium (liquid immersion exposure liquid) of at least the photoresist film between the lens and the photoresist film on the substrate, between the lens and the photoresist film on the substrate, in a pure water or a fluorine-based inert liquid having a locking thickness. )By. In this method, the exposure light path space of an inert gas such as air or nitrogen is replaced by a liquid having a large refractive index (η ), such as pure water, and even a light source of the same exposure wavelength can be used, and a shorter wavelength can be used. In the case of a light source or in the case of using a sorghum lens, high resolution can be achieved as well as a depth of focus. When such a liquid immersion exposure is used, since -6 - 201013309 is attached to a lens of a conventional apparatus, it is possible to realize a photoresist pattern which is more excellent in resolution and excellent in depth of focus at a low cost. At present, polymers, additives, and the like for use in such immersion exposure are also proposed (see Patent Documents 1 to 3). However, in the liquid immersion exposure process, when the photoresist is directly exposed to the liquid immersion liquid such as water during the exposure, the acid generator is dissolved by the photoresist film. When the amount of the eluted material is large, there is a problem that the lens is damaged or the shape of the shaped φ is not obtained, or sufficient resolution cannot be obtained. When water is used for the liquid for immersion exposure, when the water of the photoresist film has a low back contact angle and high-speed scanning exposure, the liquid for immersion exposure such as water at the end of the wafer overflows or falls, or the water is not removed. When it is completely, there is a residue of water marks (drop marks) (water mark defect), and the solubility of the film is lowered by the penetration of water into the photoresist film, and the pattern of the original image can be partially unable to achieve sufficient resolution. There are problems in the development of image defects such as poor residual defects in the shape of the pattern. In addition, even when the photoresist of the resin or the additive shown in Patent Documents 1 to 3 is used, the contact angle between the photoresist film and the water is not necessarily sufficient. When scanning at high speed, water is likely to be generated from the end of the wafer. The immersion exposure liquid overflows or falls, or has a development defect such as a water mark defect. Further, the acid generator is not sufficiently suppressed to be equal to the amount of the eluted matter in the water. In particular, as disclosed in Patent Document 3, in a system in which components having different dissolution conditions are mixed, there is a problem that the pattern shape after development is uneven. [Patent Document 1] International Publication No. 04/068, 242, Japanese Patent Application Publication No. JP-A-2005-163606, No. OBJECTS TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above circumstances. The object of the present invention is to provide high transparency to radiation, excellent sensitivity as a photoresist, and the like, while minimizing the size (collapse). A method of forming a linear radiation-sensitive resin composition, a polymer, and a photoresist pattern for liquid immersion exposure which is excellent in 'extra' immersion exposure. [Means for Solving the Problem] The present invention is as follows. [1] A sensitive radiation linear resin composition for liquid immersion exposure, which comprises (A) a resin component, a @ (B) radiation sensitive linear acid generator, and (C) a solvent-sensitive radiation linear resin composition, which is characterized by The resin component (A) contains the acid-dissociable group-containing resin (A1) containing a repeating unit (al) having a fluorine atom and an acid-dissociable group in the side chain when the resin component (A) is 100% by mass as a whole. More than 50% by mass. [2] The sensitive radiation linear resin composition for liquid immersion exposure according to the above [1], wherein the acid-dissociable group-containing resin (A1) contains a repeating unit represented by the following general formula (1) as the repeating unit. (al), -8- 201013309 【化1】

Vf R3 - X - Y - Ο - R4] η Φ [In the general formula (1), η represents an integer of 1 to 3, R1, methyl, or trifluoromethyl. R2 represents a single bond, or a straight-chain, branched or cyclic saturated or η+1) valence or R3 represents a single bond, or a linear or linear valence of 1 to 20 carbon atoms. Saturated hydrocarbon group. X represents a linear or branched fluorine-extended alkyl bond or a -CO- group which is a fluorine atom or a carbon number of 2 to 20. When η is 1, R4 represents an acid dissociable plug, and R4 independently represents a hydrogen atom or an acid dissociable group, and is an acid dissociable group. [3] The sensitizing agent for liquid immersion exposure according to the above [2], wherein the acid dissociable group-containing resin (A1) contains a repeating unit represented by (1-1) as the above general formula (unit 1). [Chemical 2] is a hydrogen atom having 1 to 10 carbon atoms (unsaturated hydrocarbon group, branched or cyclic substituted methyl group; Y system represents a single ^. η is 2 or 3 and at least 1 R4 The radiant resin group has the following general formula)

201013309 [In the general formula (1-1), the η system represents an integer of 1 to 3. R1 represents a hydrogen atom, a methyl group, or a trifluoromethyl group. R3 represents a single bond or a linear, branched or cyclic saturated or unsaturated hydrocarbon group having a carbon number of 1 to 20 valence. The X system represents a methyl group substituted by a fluorine atom or a linear or branched fluorine alkyl group having 2 to 20 carbon atoms. When η is 1, R4 represents an acid dissociable group. When n is 2 or 3, R4 independently represents a hydrogen atom or an acid dissociable group, and at least one of R4 is an acid dissociable group. R5 represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having a carbon number of 3 to 10 (n+1). [4] The sensitive radiation linear resin composition for liquid immersion exposure according to the above [2] or [3], wherein the acid dissociable group-containing resin (A1) is represented by the following general formula (1-2). The repeating unit is a repeating unit represented by the general formula (1). [化3]

(1-2) [In the general formula (1-2), R1 represents a hydrogen atom, a methyl group, or a trifluoromethyl group. R6 represents a single bond or a linear, branched or cyclic saturated or unsaturated hydrocarbon group having a valence of from 1 to 20 carbon atoms. The X system represents a methyl group substituted by a fluorine atom or a linear or branched fluorine alkyl group having a carbon number of 2 to 20%. R7 represents an acid dissociable group]. [5] The radiation linear resin composition for liquid immersion exposure according to any one of the above [2] to [4], wherein the acid-dissociable group-containing resin (Al) contains the following general formula; The repeating unit represented by (1-3) is a repeating unit represented by the general formula (1). 【化4】

R6-X-Ο-R7 [In the general formula (1-3), R1 represents a hydrogen atom, a methyl group, or a trifluoromethyl group. R6 represents a single bond or a linear, branched or cyclic saturated or unsaturated hydrocarbon group having a valence of from 1 to 20 carbon atoms. The X system represents a methyl group substituted by a fluorine atom or a linear or branched fluorine alkyl group having a carbon number of 2 to 20%. R7 represents an acid dissociable group]. Φ [6] A method for forming a resist pattern, characterized in that: (1) using the sensitive radiation linear resin composition for liquid immersion exposure according to any one of the above [1] to [5], on a substrate a step of forming a photoresist film, (2) a step of performing immersion exposure on the photoresist film, and (3) a step of developing a photoresist pattern after immersion exposure to form a photoresist pattern. [7] A polymer characterized by comprising a repeating unit represented by the following general formula (1) and a repeating unit having a lactone skeleton. -11 - 201013309 【化5】

[In the general formula (1), η represents an integer of 1 to 3. R1 represents a hydrogen atom, a methyl group or a trifluoromethyl group. R2 represents a single bond or a linear, branched or cyclic saturated or unsaturated hydrocarbon group having a carbon number of 1 n (n+1). Reference R3 represents a single bond or a linear, branched or cyclic saturated or unsaturated hydrocarbon group having a carbon number of 1 to 20 and a valence of 2 to 20 carbon atoms. The X system represents a methyl group substituted by a fluorine atom or a linear or branched fluorine alkyl group having 2 to 20 carbon atoms. The γ system represents a single bond or -CO-. When η is 1, R4 represents an acid dissociable group. When η is 2 or 3, R4 each independently represents a hydrogen atom or an acid dissociable group, and at least one R4 is an acid dissociable group. [8] A sensitive radiation linear resin composition characterized by the method for forming a photoresist pattern of the following step, wherein the photoresist film for forming the photoresist film is used for forming the resistive film, and the photoresist pattern is used. The method for forming a type includes a liquid immersion exposure step of irradiating a radiation film formed on a substrate with a refractive index higher than a liquid immersion exposure liquid at an intervening wavelength of 193 nm, and exposing the exposure The radiation sensitive linear resin composition contains (A') resin component, (B) a radiation sensitive linear acid generator, and (c) a solvent. The (A') resin component contains a fluorine atom and an acid dissociable group in a side chain. The acid-dissociable group-containing resin of the repeating unit (al) (A1 -12-201013309 and the above-mentioned radiation-sensitive linear resin composition is defined by the following formula (i) is 满足KlS5, K1=F1/ F2 (i) [ Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Fi Representation by surface element analysis And calculate the

Fluorine ratio (atom%) of the outermost surface side of the photoresist film to 20% of the film thickness J (resistance of the photoresist film): spin-coating the sensitive radiation linear resin composition on the substrate, After baking for 60 seconds, a photoresist film having a thickness of about 120 nm was produced. (Surface element analysis): X-rays were irradiated to the photoresist film using a photoelectron spectrometer Φ, and the amount of secondary electrons generated was measured, and the light was measured. The amount of fluorine atoms distributed in the resist film. [9] A photoresist film characterized by a photoresist formed on a substrate in a state in which a refractive index of a liquid crystal immersion exposure liquid having a refractive index higher than 193 nm is higher than that of air. The photoresist film used in the method for forming a photoresist pattern in which the film is irradiated with radiation to expose the liquid immersion exposure step, the K2 defined by the following formula (ii) satisfies 1SK2S5, (ϋ) k2= F3/f -13- 201013309 [In the formula (ii), F3 represents the fluorine content (atom%) in the vicinity of the outermost surface of the photoresist film measured and calculated by the following surface element analysis. F4 is represented by Surface element analysis and calculation of the most surface side to film thickness of the photoresist film Fluorescence ratio (atom%) in the vicinity of 20% (surface element analysis): X-rays were irradiated to a photoresist film using a photoelectron spectroscope, and the amount of secondary electrons generated was measured, and the amount of fluorine atoms in the photoresist film was measured. [Effects of the Invention] The sensitive radiation linear resin composition of the present invention serves as an inductively active radiation, in particular, a chemically-amplified photoresist of far-ultraviolet light represented by an ArF excimer laser (wavelength: 193 nm), which has not only radiation The basic performance of the higher transparency such as transparency and sensitivity of the line is excellent in EL (exposure tolerance) when forming a line pattern, and the shape of the pattern is good, especially the line pattern (L/S pattern) is the smallest. The inch method (collapsed) is good. @ Further, the sensitive radiation linear resin composition of the present invention is very suitable for a liquid immersion exposure process (for example, when forming a photoresist pattern, a liquid having a refractive index of 193 nm higher than that of air immersion exposure liquid ( For example, water, etc.) is between the lens and the photoresist film, the process of the immersion exposure step of irradiating the radiation, etc. Further, it is also applicable to the photoresist film not forming a protective film on the photoresist film to form a photoresist pattern. The liquid immersion exposure process) has a small amount of the liquid immersion exposure liquid for the water contacted during the immersion exposure, and the liquid immersion exposure liquid of the photoresist film and the water has a large back contact angle. Increasing the solubility of the exposure portion to the developing solution-14-201013309, so that the development defects can be suppressed. In addition, the deviation of the pattern shape of the immersion exposure process can be improved. Based on the above, it is very suitable for manufacturing and is expected to be further refined in the future. MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the invention is as follows. The present invention is not limited to the embodiment of φ, and the present invention is not limited to the scope of the technical features of the present invention. The general knowledge of the artist is appropriately modified and improved. In the present specification, "(meth)acrylic acid" means acrylic acid and methacrylic acid. "(Meth)acrylate" means acrylate and methacrylate. Further, "(meth)acrylonitrile" means an acryloyl group and a methacryloyl group. [1] Linear radiation resin composition for liquid immersion exposure (I) The linear radiation resin composition for liquid immersion exposure of the present invention (hereinafter sometimes referred to simply as "sensitive radiation linear resin composition (I)") Containing (A) resin component, (B) sensitive radiation linear acid generator, (C) solvent. < (A) Resin component> The resin component (hereinafter also referred to as "resin component (A)") contains acid dissociation property containing a repeating unit (al) having a fluorine atom and an acid dissociable group in a side chain. Base resin (A1) [hereinafter sometimes referred to simply as "resin-15 - 201013309 (A1)"]. The sensitive radiation linear composition (1) of the present invention contains the resin (A1) containing the repeating unit (al) as the resin component (A). Therefore, the swelling caused by the developing liquid can be suppressed, and the pattern collapse can be improved. performance. That is, the minimum collapse size can be increased. The resin (A1) is a resin having an alkali-insoluble or alkali-insoluble property of an acid-dissociable group, and is dissociated by an acid-dissociable group to become an alkali-soluble resin. The term "alkali-insoluble or alkali-insoluble" as used herein refers to a base film formed by using a photosensitive resin composition (I) containing a @ resin component (A), which is used in forming a photoresist pattern. When the film is developed by using only the film of the resin (A1) instead of the photoresist film under development conditions, 50% or more of the initial film thickness of the film remains after development. The repeating unit (al) is not particularly limited as long as it has a fluorine atom and an acid dissociable group in the side chain, that is, a fluorine atom and an acid dissociable group in the side chain, but is, for example, the following general formula (1) The repeating unit indicated is preferred. ◎ 【化6】

(1) [In the general formula (1), η represents an integer of 1 to 3. R1 represents a hydrogen atom -16-201013309, methyl or trifluoromethyl. R2 represents a linear or branched or cyclic saturated or unsaturated hydrocarbon group having a single bond or a (n+l) valence of carbon number ι~ι. R3 represents a single bond or a linear, branched or cyclic saturated or unsaturated hydrocarbon group having a carbon number of 1 to 20 valence. The X system represents a methyl group substituted by a fluorine atom or a linear or branched fluorine alkyl group having 2 to 20 carbon atoms. The Y system represents a single bond or -CO-. When η is 1, R4 represents an acid dissociable group. When n is 2 or 3, R4 independently represents a hydrogen atom or an acid dissociable group, and at least one R4 # acid dissociable group. a linear or branched saturated or unsaturated hydrocarbon group having a carbon number of from 1 to 10 (n = 1) in R2 of the above general formula (1), for example, a methyl group, an ethyl group, or a η-propyl group. Base, i-propyl, η-butyl, 2-methylpropyl, 1-methylpropyl, butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, decyl And a divalent hydrocarbon group derived from a linear or branched alkyl group having 1 to 10 carbon atoms, such as a mercapto group. The cyclic saturated or unsaturated hydrocarbon group ' in the valence (n = 1) of R2 in the above general formula (1) is, for example, a group derived from an alicyclic hydrocarbon having 3 to 10 carbon atoms and an aromatic hydrocarbon. The aforementioned alicyclic hydrocarbons are, for example, cyclobutane, cyclopentane, cyclohexane, bicyclo[2·2·1]heptane, bicyclo[2.2.2]octane, tricyclo[5.2.1.02,6]癸a naphthane such as an alkane or a tricyclo[3·3·1.13,7]decane. Examples of the aromatic hydrocarbon include benzene and naphthalene. The hydrocarbon group in the above R2 may be at least one hydrogen atom of the above unsubstituted hydrocarbon group by a methyl group, an ethyl group, a η-propyl group, an i-propyl group, an η-butyl group, a 2-methyl thio group, 1_ A linear or branched -17-201013309 or a cyclic alkyl group, a hydroxyl group, a cyano group, a hydroxyalkyl group having 1 to 10 carbon atoms, or a carboxyl group having a carbon number of 1 to 4, such as a methylpropyl group and a t-butyl group. One or two or more substituents substituted with an oxygen atom or the like. When R2 is trivalent (n = 2) and tetravalent (n = 3), for example, each of the divalent hydrocarbon groups has a hydrogen atom desorbed from the group and the divalent hydrocarbon group has two hydrogen atoms. The basis of separation. The linear or branched saturated or unsaturated hydrocarbon group having a carbon number of 1 to 20 in the above R3 of the general formula (1), for example, a methyl group, an ethyl group, an η-propyl group, an i-propyl group Base, η-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, φ pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, decyl, hydrazine A divalent hydrocarbon group such as a linear or branched alkyl group having a carbon number of 1 to 20 or the like. The divalent cyclic saturated or unsaturated hydrocarbon group in R3 of the above general formula (1) is, for example, a group derived from an alicyclic hydrocarbon having 3 to 20 carbon atoms and an aromatic hydrocarbon. The aforementioned alicyclic hydrocarbons are, for example, cyclobutane, cyclopentane, cyclohexane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, tricyclo[5.2.1.02'6]nonane, a cycloalkane such as tricyclo[3.3.1.13,7]decane, tetracyclo[6·2·1.13,6.〇2,7]dodecane.前述 The above aromatic hydrocarbons are, for example, benzene, naphthalene or the like. The hydrocarbon group in the above R3 may be at least one nitrogen atom of the above unsubstituted hydrocarbon group, which is methyl, ethyl, η-propyl, i-propyl, η-butyl, 2-methylpropyl, 1- a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms such as methyl propyl or t-butyl, a hydroxy group, a cyano group, a hydroxyalkyl group having a carbon number of 10, a carboxyl group, an oxygen atom, or the like. One or two or more substituted groups. Further, when the η of the general formula (1) is 2 or 3, the above R3 may be all the same groups or a part or all of the different groups. -18 - 201013309 The acid dissociable group in R4 of the above general formula (1) means a group which is substituted with a hydrogen atom in an acidic functional group such as a hydroxyl group, a mercapto group or a sulfonic acid group, and is dissociated in the presence of an acid. Base. Such acid-cleavable groups are, for example, t-butoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, (thiotetrahydropyranylsulfonyl)methyl, (thiotetrahydrofuranylsulfonyl)methyl Or an alkoxy-substituted methyl group, an alkylsulfonyl group-substituted methyl group or the like. The alkoxy group (substituent) in the alkoxy group-substituted methyl group is, for example, an alkoxy group having 1 to 4 carbon atoms. Further, the alkyl group (substituent) in the alkyl group substituted with a methyl group is, for example, an alkyl group having 1 to 4 carbon atoms. The acid dissociable group is, for example, a group represented by the general formula [-C(R) 3] (wherein three R groups independently represent a linear or branched alkyl group having a carbon number of 1 to 4, and a carbon number; a monovalent alicyclic hydrocarbon group of 4 to 20 or a group derived therefrom, or any two of R groups bonded to each other, together with a carbon atom bonded thereto, together form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or the same The derivatized group, the remaining R is a linear or branched alkyl group having a carbon number of 1 to 4, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a group derived therefrom. The linear or branched alkyl group having 1 to 4 carbon atoms of R in the acid dissociable group represented by the above general formula [-C(R)3], for example, methyl group, ethyl group, η-propyl group , i-propyl, η-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, etc., a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms of the above R, for example, having a norbornene An alicyclic ring derived from a cycloalkane or the like, such as an alkane, a tricyclodecane, a tetracyclododecane, an adamantane, a cyclobutane, a cyclopentane, a cyclohexane, a cycloheptane or a cyclooctane. 19-201013309 Ke et al. The group derived from the alicyclic ring is, for example, the above monovalent alicyclic hydrocarbon group such as methyl, ethyl, η-propyl, i-propyl, η-butyl, 2-methylpropyl. And one or more or more substituted groups of a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms such as a methyl propyl group or a t-butyl group. Among these, the alicyclic hydrocarbon group of R is preferably an alicyclic hydrocarbon group composed of an alicyclic ring derived from norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane or cyclohexane or the like. The alicyclic hydrocarbon group is substituted with the aforementioned alkyl group or the like. Any two R groups are bonded to each other, and a carbon atom (a carbon atom bonded to an oxygen atom) bonded thereto is formed together to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, for example, a cyclobutyl group, a cyclopentyl group, and a stretching group. A cyclohexyl group, a cycloheptyl group, a monocyclic hydrocarbon group of a cyclooctyl group, a borneol group, a tri-cyclohexyl group, a polycyclic hydrocarbon group of a tetra-cyclohexyl group, and a crosslinked polycyclic hydrocarbon group of an adamantyl group. R is a group derived from a divalent alicyclic hydrocarbon group formed by bonding with each other, and for example, the above-mentioned divalent alicyclic hydrocarbon group is, for example, methyl, ethyl, n-propyl, i-propyl, η-butyl, 2 - one or more or one or more substituted groups of a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms such as a methylpropyl group, a 1-methylpropyl group or a t-butyl group; Wait. Among these, a monocyclic hydrocarbon group which is a cyclopentyl group or a cyclohexyl group or a group in which the divalent alicyclic hydrocarbon group (monocyclic hydrocarbon group) is substituted with the aforementioned alkyl group or the like is preferable. Preferred examples of the acid dissociable group represented by the general formula [-C(R)3] are t-butyl, ln-(1-ethyl-1-methyl)propyl, ln-(1,1_ Methyl)propyl, ln-(l,l-dimethyl)butyl, 1-η-(ΐ,ι·dimethyl)pentyl, 1-(1,1-diethyl)propyl , 1-n-( 1,1-diethyl)butyl, -20- 201013309 1-11-(1,1-diethyl)pentyl, 1-(1-methyl)cyclopentyl, 1 -(1-ethyl)cyclopentyl, 丨-丨1-11-propyl)cyclopentyl, propyl)cyclopentyl, 1-(1-methyl)cyclohexyl, 1-(1-ethyl Cyclohexyl, i-(in-propyl)cyclohexyl, i-Ci-i-propyl)cyclohexyl, 1-(1-methyl-1-(2-norbornyl)}ethyl, 1- {1-Methyl-1-(2-tetracycloindenyl)}ethyl, 1-{1-methyl-1-(1-adamantyl)}ethyl, 2-(2-methyl)-lower Borneol base, 2-(2-ethyl)norbornyl, 2-(2-n-propyl)norbornyl, 2-φ(2-i-propyl)norbornyl, 2-(2-A Tetracycline, 2-(2-ethyl)tetracyclodecyl, 2-(2-η-propyl)tetracyclodecyl, 2-(2-i-propyl)tetracyclodecyl, 1-(1-methyl)adamantyl, 1-(1-ethyl)adamantyl ' 1 - ( 1 -η-propyl a group consisting of adamantyl, 1-(1-i-propyl)adamantyl or some alicyclic ring, for example, methyl, ethyl, η-propyl, i-propyl, η- One or more or more of linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms such as butyl, 2-methylpropyl, 1-methylpropyl or t-butyl. The group to be substituted, etc. Φ Among these acid-dissociable groups, a group represented by the above [-C(R)3], a t-butoxycarbonyl group, an alkoxy-substituted methyl group, etc. are preferable. (1) When a hydroxyl group is protected, a t-butoxycarbonyl group or an alkoxy group-substituted methyl group is preferred, and (2) when a carboxyl group is protected, a group represented by [-C(R)3] is preferred. (1) A methyl group substituted by a fluorine atom in X, or a linear or branched fluorine alkyl group having 2 to 20 carbon atoms, for example, the following (X-1) to (X-8) Structure], etc. -21 - 201013309 [Chem.7] F3C F3C-C-CF3 f3c c--cf3 c——cf3 F3C-C-CF3 f3c—·c—cf3 F3C-C-CF3 (X-1) ( X-2) (X-3) f3c-c-cf3 f3c——c——cf3 f3c——c——cf3 f3c——c——cf3 I(X-4)

F-C ~F (X - 5)

F——C——F F——C——F (X-6)

F——C——F F C-F

I

F-C-F

I (X-7)

F——C——FF——C——FF——C——FF——C——F (X-8) The above-mentioned general formula (1) represents a repeating unit, for example, the following general formula (1) 1) Repetitive units indicated. 【化8】

(1-1) [In the general formula (1-1), the η system represents an integer of 1 to 3. R1 represents hydrogenogen-22-201013309, methyl, or trifluoromethyl. R3 represents a single bond or a linear, branched or cyclic saturated or unsaturated hydrocarbon group having a carbon number of 1 to 20 valence. The x series represents a methyl group substituted by a fluorine atom or a linear or branched fluorine alkyl group having 2 to 20 carbon atoms. When η is 1, R4 represents an acid dissociable group. When η is 2 or 3, R4 independently represents a hydrogen atom or an acid dissociable group, and at least one of R4 is an acid dissociable group. R5 represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having a carbon number of 3 to 10 (η+1). • The descriptions of R3, R4, and X of the above general formula (1) are directly applied to R3, R4, and X of the above general formula (1-1). a linear or branched saturated or unsaturated hydrocarbon group having a carbon number of 3 to 10 (n = 1) in R5 of the above general formula (1-1), for example, η-propyl, i- Propyl, η-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, decyl, hydrazine A divalent hydrocarbon group derived from a linear or branched alkyl group having 3 to 10 carbon atoms or the like. The cyclic • saturated or unsaturated hydrocarbon group of the valence (n=l) of R5 in the above general formula (1-1), for example, an alicyclic hydrocarbon derived from a carbon number of 3 to 10 and an aromatic hydrocarbon group . The aforementioned alicyclic hydrocarbons are, for example, cyclobutane, cyclopentane, cyclohexane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, tricyclo[5.2.1.02,6]nonane, a cycloalkane such as tricyclo[3.3.1.13'7] decane. Examples of the aromatic hydrocarbon include benzene and naphthalene. The hydrocarbon group in the above R5 may be at least one hydrogen atom of the above unsubstituted hydrocarbon group, which is methyl, ethyl, n-propyl, i-propyl, η-butyl, 2-methylpropyl, 1- a linear or branched -23-201013309 or a cyclic alkyl group, a hydroxyl group, a cyano group or a hydroxyalkyl group having a carbon number of 1 to 4, such as a methyl propyl group or a t-butyl group; One or two or more substituents substituted with a carboxyl group or an oxygen atom. When R5 is trivalent (n=2) and tetravalent (n=3), for example, each of the divalent hydrocarbon groups has a hydrogen atom desorbed from the group and the divalent hydrocarbon group has two hydrogen atoms. The basis of separation. In the above-mentioned repeating unit represented by the general formula (1-1), it is preferred that the following formula (1-la) ~ (l-lf) represents a repeating unit or the like, and particularly preferably the following general formula ( ld-Ι) indicates the repeating unit. 【化9】

(1-M) (1-1e) (1-tf) In the general formula (l-ia) to (1-lf), η represents an integer of 1 to 3. The Ri system represents a hydrogen atom, a methyl group, or a trifluoromethyl group. When η is 1, R4 represents an acid-dissociable group. When ri is 2 or 3, R4 independently of each other means a hydrogen atom or an acid dissociates from -24 to 201013309, and at least one R4 is an acid dissociable group] [Chemical 1 0]

[In the general formula (:l-ld-1), R4 independently represents a hydrogen atom or an acid dissociable group, and at least one R4 is an acid dissociable group] The above general formula (Ι-la)~(Ι-lf And R4 of (l-ld-Ι) can directly apply the description of R4 of the above general formula (1). The repeating unit represented by the above general formula (1) is, for example, a repeating unit represented by the following general formula (1-2). ❿ 【化1 1】

[In the general formula (1-2), R1 represents a hydrogen atom, a methyl group, or a trifluoromethyl group. R6 represents a single bond or a linear or branched chain of -25 to 201013309 having a carbon number of 1 to 20 or a cyclic saturated or unsaturated hydrocarbon group. The fluorene series means a methyl group substituted by a fluorine atom or a linear or branched fluorine alkyl group having 2 to 20 carbon atoms. R7 represents an acid dissociable group]. The X, R6 and R7 in the general formula (1-2) can be directly applied to the description of the acid dissociable groups of X, R3 and R4 in the above general formula (1).

Specific examples of R6 in the general formula (1-2) have the following structures: (a27) and the like. The "*" in the structure (al) to (a27) indicates the binding site. [1 2]

(al ) (a2 ) ( a3 )

(a15) ( at6 )

(a17) (a!8)

(a19)

(a20)

(a22) (a23)

(a25) (a26) (a27) -26- 201013309 R6 in the general formula (1-2) is, for example, a methyl group, an ethyl group, a methyl group, a methyl group, a 2-methyl group, a carbon number of 4~ The 20-valent alicyclic hydrocarbon group or such derived groups and the like are preferred. R7' in the general formula (1-2) is preferably, for example, a t-butoxycarbonyl group or an alkoxy-substituted methyl group, or a group represented by the above general formula [-C(R)3]. The repeating unit represented by the above general formula (1) is, for example, a repeating unit represented by the following general formula (1-3). 【化1 3】

(1-3) [In the general formula (1-3), R1 represents a hydrogen atom, a methyl group, or a trifluoromethyl group. R6 represents a single bond or a linear, branched or cyclic saturated or unsaturated hydrocarbon group having a carbon number of 1 to 20 and a linear value. The X system represents a methyl group substituted by a fluorine atom or a linear or branched fluorine alkyl group having 2 to 20 carbon atoms. R7 represents an acid dissociable group]. The X and R7 in the general formula (1-3) can be directly applied to the description of the acid dissociable group of X and R4 in the above general formula (1). Further, R6 in the general formula (i.3) can directly apply the description of R6 in the above general formula (1-2). The resin (A1) may contain only one type or two or more types of repeating units (al) represented by the general formula (1). -27- 201013309 The content of the repeating unit (al) is preferably from 3 to 50 mol%, more preferably from 5 to 30, when the total of all the repeating units contained in the resin (A1) is 100 mol%. Mo. _If the order $(...$ contains more than 50% of the %, it may cause the solubility in the developing solution to be affected by the exposure ,, and the resolution will deteriorate. If it is less than 3 旲%, 'may not be obtained. Further, the resin (A1) contains, in addition to the above repeating unit (al), another repeating unit, for example, a repeating unit having an acid dissociable group (except for the repeating unit (al)) A repeating unit having a lactone skeleton, a hydroxyl group, a carboxyl group or the like is preferably used to increase alkali solubility. A repeating unit having an acid dissociable group (hereinafter referred to as "repeating unit (a2)")" has, for example, (meth)acrylic acid t- Butyl ester, (methyl)-propyl citrate 1-methyl-1-cyclopentyl ester, (methyl)-propyl citrate 1-ethyl-1-cyclopentaacetic acid, 1-isopropyl-(meth)acrylate- 1-cyclopentyl ester, 1-methyl-1-cyclohexyl (meth)acrylate, 1-ethyl-1-cyclohexyl (meth)acrylate, 1-isopropyl-1(meth)acrylate -cyclohexyl ester, 1-ethyl-1-cyclooctyl (meth)acrylate, 2·methyladamantyl-2-yl (meth)acrylate, 2-ethyladamantane (meth)acrylate Base-2- Base ester, 2_n-propyladamantyl-2-yl (meth)acrylate, 2-isopropylidenyl-2-yl (meth)acrylate, 1-(adamantane) (meth)acrylate · 1-yl)-1-methylethyl ester, 1-(adamantan-1-yl)-1-ethylethyl (meth)acrylate, 1-(adamantan-1-yl) (meth)acrylate -1-methylpropyl ester, 1-(adamantan-1-yl)-1-ethylpropyl (meth)acrylate, etc. Among them, (meth)acrylic acid, methyl-1-cyclopentyl ester, (Methyl 201013309) 1-ethyl-1-cyclopentyl acrylate, 1-isopropyl-1-cyclopentyl (meth)acrylate, 1-methyl-1-cyclohexyl (meth)acrylate, 1-ethyl-1-cyclohexyl (meth)acrylate, 1-isopropyl-1-cyclohexyl (meth)acrylate, 1-ethyl-1-cyclooctyl (meth)acrylate, etc. The repeating unit of the acid-dissociable group of the monocyclic ring. The resin (A1) may contain only one type or two or more types of repeating units (a2) having an acid-dissociable group. When the total of all repeating units contained in the resin (a 1 ) is 1% mol%, It is 1〇~9〇mol%, more preferably 20~80mol%. When the content of the repeating unit (a2) is less than 10旲%, it may affect the dissolution of the developing solution after exposure. The solubility is deteriorated, and when it exceeds 80 mol%, the adhesion to the substrate may be insufficient. The monomer having the repeating unit containing the lactone skeleton (hereinafter referred to as "repeating unit (a3)") is generated. For example, the following general formula (21) ~ (2_6 •), etc. -29- 201013309 [Chemical 1 4]

(2-Ή

[In the general formula (2-1) to (2-6), R11 represents a hydrogen atom or a methyl group. R12 represents a hydrogen atom or an alkyl group having a substituent of carbon number 1 to 4, and a Ri3 hydrogen atom or Methoxy. A represents a single bond, an ether group, an ester group, a carbonyl group, a divalent chain hydrocarbon group having 1 to 3 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, and a divalent aromatic hydrocarbon having 6 to 3 carbon atoms. A hydrocarbon group or a combination of these two valent groups, and B represents an oxygen atom or a methyl group. 1 is an integer of 1 to 3 'm system or 1'. In the above R12 of the general formula (2_丨), an alkyl group having a substituent of 1 to 4, for example, a methyl group, an ethyl group, or a n group Propyl, decyl propyl, η butyl, 2-methylpropyl, hydrazine methyl propyl, butyl butyl and the like. The carbon number in the general formula (2_2) and (2-3) is 1 to 30 2 -30- 201013309 The valence chain hydrocarbon group 'for example, methyl group, ethyl group, 1, 2 - stretching Propyl, 1,3 -propyl, butyl, pentyl, hexyl, heptyl, octyl, hydrazine, hydrazine, eleven, and twelve a linear alkyl group such as a tribasic group, a fourteenth base group, a fifteenth base group, a thirteenth base group, a thirteenth base group, a thirteenth base group, a tenteenth base group, and a twenty base group; -1,3-propanyl, 2-methyl-1,3-propanyl, 2-methyl-1,2-propanyl, 1-methyl-1,4-butylene, 2- A branched alkyl group such as a methyl-1,4-butylene group, a methylene group, an ethylene group, a propylene group or a 2-propylene sulfide group. The carbon number of A in the above general formulas (2-2) and (2-3) is a 3 to 30 alicyclic alicyclic hydrocarbon group, for example, a 1,3-cyclopentene butyl group or the like, and a 1,3-cyclopentene group a monocyclic cycloalkyl group having a carbon number of 3 to 30, such as a 1,4-cyclohexylene group, a 1,5-cyclohexyl group, or the like; 1,4 - an extended borneol group, a 2,5-extension A polycyclic cycloalkylene group such as a borneol group, a 1,5-adamantyl group, a 2,6-adamantyl group or the like. The divalent aromatic hydrocarbon group having a carbon number of 6 to 30 in the above general formulae (2-2) and (2-3) is, for example, a phenyl group, a tolyl group, an anthranyl group, a phenanthrene group, Stretching bases, etc. Specific examples of preferred monomers for providing the above repeating unit (a3) are, for example, (meth)acrylic acid-5-oxy-4-oxa-tricycloindole·2·1.03'7]non-2-yl ester , (meth)acrylic acid-9-methoxycarbonyl-5-oxy-4-oxa-tricyclo[4.2.1_03,7]壬_2-yl ester, (meth)acrylic acid-5-oxyl 4-oxa-tricyclo[5.2.1.03,8]non-2-yl ester, (meth)acrylic acid-10-methoxycarbonyl_5-oxy-4-oxa-tricyclo[5.2. 1. 〇3,8]non-2-yl ester, (meth)acrylic acid-6-oxy-7-oxa-bicyclo[3.2.1]oct-2-yl ester, (meth)acrylic acid 4-methoxycarbonyl-6-oxy·7.oxa-bicyclo[3.2.1]oct-2-yl ester, 201013309 (methyl)acrylic acid-7-oxy-8-oxa-bicyclo[ 3.3.1] Oct-2-yl ester, (meth)acrylic acid _4-methoxycarbonyl-7-oxy-8-oxa-bicyclo[3.3.1]oct-2-yl ester, (methyl Acetic acid-2-oxytetrahydropyran-4-yl ester, (meth)acrylic acid-4-methyl-2-oxytetrahydropyran-4-yl ester, (meth)acrylic acid-4- Ethyl-2-oxytetrahydropyran-4-yl ester, 4-methyl-2-oxytetrahydropyran-4-yl (meth)acrylate, (meth) propylene -5-oxytetrahydrofuran-3-yl ester, (meth)acrylic acid-2,2-dimethyl-5-oxytetrahydrofuran-3-yl ester, (meth)acrylic acid-4,4-dimethyl -5-oxytetramethanesulfan-3-yl ester, (meth)acrylic acid-2-oxytetrahydrofuran-3-yl ester, (meth)acrylic acid _4,4-dimethyl-2-oxytetrahydrofuran 3-yl ester, 5,5-dimethyl-2-oxytetrahydrofuran-3-yl (meth)acrylate, 2-oxytetrahydrofuran-3-yl (meth)acrylate, (methyl) Acetyl-5-oxytetrahydrofuran-2yl methyl ester, (meth)acrylic acid-3,3-dimethyl-5-oxytetrahydrofuran-2-ylmethyl ester, (meth)acrylic acid_4,4 - dimethyl-5-oxytetrahydrofuran-2-yl ester and the like. The resin (Α1) may contain only one type or two or more types of repeating units (a3) having an acid dissociable group. The ratio of the content of the repeating unit (a3) is preferably 10 to 85 moles/〇' more preferably 10 to 70 moles when the total of all repeating units contained in the resin (Ai) is 10% by mole. The ear 'better is 15 to 60 mol%. When the content ratio of the repeating unit (a3) is less than 5 mol/0, the developing property and the exposure tolerance tend to deteriorate. On the other hand, when it exceeds W mole%, the solubility of the resin (A1) in the solvent is deteriorated, and the degree of dissociation tends to be deteriorated. The resin (A1) of the present invention may contain a repeating unit containing an alicyclic compound or a repeating unit derived from an aromatic compound, in addition to the above-mentioned repeating units - (a2) and (a3) of -32-201013309. The repeating unit (hereinafter referred to as "repeating unit (a4)") containing the alicyclic compound is, for example, a repeating unit derived from a monomer represented by the following general formula (3). [化1 5]

(3) In the general formula (3), R14 represents a hydrogen atom, a methyl group or a trifluoromethyl group, and X represents an alicyclic hydrocarbon group having 4 to 20 carbon atoms. The alicyclic hydrocarbon group having 4 to 20 carbon atoms in the above X of the general formula (3), for example, cyclobutane, cyclopentane, cyclohexane, bicycloindole 2·2·1] heptane, bicyclo φ [2.2.2] Octane, tricyclo[5.2.1 ·〇2,6]decane, tetracyclo[6.2.1. 13'6.〇2'7] dodecane, tricyclo[3.3.1 · 13'7] a hydrocarbon group derived from an alicyclic ring of a cycloalkane such as decane. The alicyclic ring derived from these cycloalkanes may have a substituent such as methyl, ethyl, η-propyl, i-propyl, η-butyl, 2-methylpropyl, 1-methylpropyl, One or more of the linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms such as a butyl group or the like are substituted. These are not limited to those substituted by these alkyl groups, and may be substituted by a hydroxyl group, a cyano group, a hydroxyalkyl group having 1 to 10 carbon atoms, a ketone group or an oxygen atom. -33- 201013309 Preferred monomers of the above repeating unit (a4) are provided, for example, (meth)acrylic acid-bicyclo[2.2.1]hept-2-yl ester, (meth)acrylic acid_bicyclo[2.2.2 Octyl-2-ester, (meth)acrylic acid, tricyclo[5.2.1.〇2,6]癸_7_yl ester, (meth)acrylic acid-tetracyclo[6_2.1.13'6.〇2' 7] Twelve _9_ based vinegar, (meth)acrylic acid-tricyclo[3.3.1.13'7]non-1-yl ester, (meth)acrylic acid-tricyclo[3·3.1·ι3'7]癸-2_yl ester and the like.

The resin (Α1) may contain only one kind of or more than two or more repeating units (a4) represented by the formula (1). The ratio of the content of the repeating unit (a4) is preferably 30 mol% or less, more preferably 25 mol% or less, when the total of all repeating singles contained in the resin (A1) is 100 mol%. The content of this repeating unit (a4) exceeds 30%. / ctti

At the time of the ear, the shape of the photoresist pattern may deteriorate or the resolution may decrease. Preferred monomers derived from the repeating unit of the aromatic compound (hereinafter referred to as "^ complex" (a5)") are, for example, styrene, α-methylstyrene, 2-methylstyrene, 3 _Methylstyrene, 4-methylstyrene, 2-methoxybenzene 4, 3-methoxyphenylethyl, *•methoxystyrene, 4_j2·butoxycarbonylethoxy) Styrene, h-hydroxystyrene, h-hydroxystyrene, 4'-p-styrene, 2-trans-yl.α-methylstyrene, 3-hydroxyl-α-methyl-ethylene, 4·hydroxy-α-methyl Styrene, 2-methyl_3_hydroxyphenylethyl, 4 _ Tianqi, - Xiangji styrene, 5-methyl-3-hydroxystyrene, 2-methyl-4- ke, lean, · b Anthene ethylene, 3-methyl-4-hydroxysilane, 3,4-dihydroxystyrene 2'4'6-hydroxystyrene, 4_t-butoxystyrene, deuterated butyoxy alpha-methylbenzene Ethylene, 4-(2-ethyl.2-propoxy)styrene, 4-(2-ethyl-2-propoxy)-α, styrene, 4_(]·ethoxyethoxy) Benzene-34- 201013309 Ethylene, 4-(1-ethoxyethoxy)_α-methylstyrene, phenyl (meth)acrylate, (meth)acrylic acid Benzyl ester, terpene, 5-hydroxyl dilute, b-ethylnaphthalene, 2-ethylenylnaphthalene, 2-carbyl-6-ethyl-naphthyl naphthalene, 1-naphthyl (meth)acrylate, (methyl 2-naphthyl acrylate, (meth) acrylate, naphthyl methyl ester, decyl decyl (meth) acrylate, 2- decyl (meth) acrylate, 9- decyl (meth) acrylate, (meth)acrylic acid 9-fluorenylmethyl ester, 1-ethyl sulfhydryl hydrazine, and the like. The resin (A1) may contain only one type or two or more types of repeating units (a5) represented by the formula (1). When the total content of all the repeating units contained in the resin (A1) is 1% by mole, the content of the repeating unit (a5) is preferably 4% by mole or less, and more preferably 30% by mole or less. . The content of this repeating unit (a5) exceeds 40 moles. /. When the radiation transmittance is lowered, the shape of the pattern may be deteriorated, and the resin (A1) of the present invention may further contain other repeating units in addition to the other repeating units [heavy-parallel units (a2) to (a5)]. (hereinafter referred to as "other additional repeating units"). The "other additional repeating unit" includes, for example, a (meth) acrylate having a bridged hydrocarbon skeleton such as dicyclopentanyl (meth) acrylate or adamantyl (meth) acrylate: (methyl) a carboxyl group-containing ester having a bridged hydrocarbon skeleton; an unsaturated carboxylic acid such as carboxynorbornyl acrylate, carboxytricyclodecyl (meth) acrylate or carboxytetracycloundecyl (meth) acrylate; Methyl)methyl acrylate, ethyl (meth) acrylate, (methyl-35-201013309) η-propyl acrylate, η-butyl (meth) acrylate, 2-methylpropyl (meth) acrylate , 1-methylpropyl (meth)acrylate, t-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid 3-hydroxypropyl ester, cyclopropyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-methoxycyclohexyl (meth)acrylate, (methyl) ) 2-cyclopentyloxycarbonylethyl acrylate, 2-cyclohexyloxycarbonylethyl (meth)acrylate, (meth)acrylic acid 2 -(4-methoxycyclohexyl)oxycarbonylethyl ester or the like (meth) acrylates having no bridge@ hydrocarbon skeleton; α-hydroxymethyl methacrylate, α-hydroxyethyl methacrylate , α-hydroxymethyl acrylate such as α-hydroxymethyl methacrylate η-propyl ester, α-hydroxymethyl methacrylate η-butyl ester; (meth)acrylonitrile, α-chloroacrylonitrile, crotononitrile, horse Unsaturated nitrile compound such as nitrile, fumaronitrile, mesocarbonitrile, citraconazole, ikononitrile, etc.; (meth) acrylamide, hydrazine, hydrazine-dimethyl (meth) acrylamide, croton Unsaturated guanamine compounds such as amine, maleimide, fumarine, mesaconamine, cimolamide, ikonium amide, etc.; Ν-(meth) propylene hydrazino porphyrin, hydrazine-ethylene Other nitrogen-containing vinyl compounds such as keto-ε-caprolactam, fluorene-vinylpyrrolidone, vinylpyridine, vinylimidazole, etc.; (meth)acrylic acid, crotonic acid' maleic acid, maleic anhydride, fumar Unsaturated carboxylic acids (anhydrides) such as acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, meconic acid, etc.; 2-carboxyethyl (meth)acrylate, (methyl) 2-carboxypropyl acrylate, 3-carboxypropyl (meth)acrylate, 4-carboxybutyl (meth)acrylate, 4-carboxycyclohexyl (meth)acrylate, etc. without unsaturated carboxylic acid Carboxyl esters having a bridged hydrocarbon skeleton: -36- 201013309 12-adamantanediol di(meth)acrylate; [,3_adamantanediol-(meth)acrylate,-adamantane II a polyfunctional monomer having a bridged hydrocarbon skeleton such as an alcohol di(meth)acrylate or a tricyclodecyldimethylol di(meth)acrylate; methyl glycol di(meth)acrylate, B Diol di(meth)acrylate, propylene glycol di(meth)acrylate, 1ί6_hexanediol di(meth)acrylate, 2,5-dimethyl-2,5-hexanediol di(a) Acrylate #,丨,8·octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,4-bis(2-hydroxypropyl)benzene Polymerization of a polyfunctional monomer such as a polyfunctional monomer having no bridge hydrocarbon skeleton such as (meth) acrylate or 1,3-bis(2-hydroxypropyl)benzenedi(meth)acrylate Sexually unsaturated The key is cleaved by the unit. Among these other additional repeating units, a unit having a polymerizable unsaturated bond having a (meth) acrylate having a bridged hydrocarbon skeleton is preferably cleaved. Φ The above resin (Α1) may contain only one type or two or more other repeating units. The content ratio of the other additional repeating unit is preferably 50 mol% or less, more preferably 40 mol% or less, when the total of all the repeating units contained in the resin (?1) is 100 mol%. Further, the resin (A 1 ) of the present invention can be used, for example, by using a hydroperoxide, a dialkyl peroxide or a dimercapto group as a polymerizable unsaturated monomer corresponding to each repeating unit. A radical polymerization initiator such as an oxide or an azo compound is produced by performing polymerization in a solvent of an appropriate -37 to 201013309 as needed in the presence of a chain transfer agent. The solvent used for the polymerization is, for example, an alkane such as η-pentane, η-hexane, η-heptane, η-octane, η-decane or η-decane; cyclohexane or cycloheptane. Naphthenes such as cyclooctane, decahydronaphthalene, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutanes, bromohexanes, dichloro Halogenated hydrocarbons such as ethane, hexamethylene dibromide and chlorobenzene; saturated carboxylic acid esters such as ethyl acetate, η-butyl acetate, i-butyl acetate, methyl propionate; acetone; A ketone such as 2-butanone, 4-methyl-2-pentanone or 2-heptanone; an ether such as tetrahydrofuran, dimethoxyethane or diethoxyethane; and the like. These solvents may be used alone or in combination of two or more. The reaction temperature of the above polymerization is usually from 40 to 150 ° C, preferably from 50 to 120 ° C, and the reaction time is usually from 1 to 48 hours, preferably from 1 to 24 hours. Further, the polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") measured by the gel permeation chromatography (GPC) method of the resin (A1) of the present invention is not particularly limited, but is preferably 1,000 to 100,000, more preferably It is 1,000 to 30,000, and the best is 1,000 to 20,000. When the Mw of the resin (A1) is less than 1,000, the heat resistance as a photoresist tends to be lowered. On the other hand, when the Mw exceeds 100,000, the developability as a photoresist tends to decrease. Further, the ratio (Mw/Mn) of the Mw of the resin (A1) to the polystyrene-equivalent number average molecular weight (hereinafter referred to as "Μη") of the GPC method is usually 1 to 5, preferably 1 to 3. In the resin (A1), the content of the low molecular weight component derived from the monomer used in the preparation of the resin (A1) is preferably 10% by mass, preferably 〇% by mass based on -38 to 201013309. 1% by mass or less is more preferably 0. 0 7 mass% or less, still more preferably 0.05 mass% or less. When the content is 0.1% by mass or less, the amount of the eluted material in the liquid for immersion exposure such as water contacted during liquid immersion exposure can be reduced. Further, in the storage of the photoresist, foreign matter does not occur in the photoresist, and even when the photoresist is applied, coating unevenness does not occur, and defects occurring during formation of the photoresist pattern can be sufficiently suppressed. The low molecular weight component derived from the monomer may be, for example, a monomer, a dimer, a Φ trimer or an oligomer, and may be a component having a MW of 500 or less. The components below this MW500 can be removed, for example, by the following purification method. The amount of this low molecular weight component can be analyzed by high speed liquid chromatography (HPLC) of the resin. The resin (A1) is preferably as small as the content of impurities such as a halogen or a metal, whereby the sensitivity, resolution, process stability, and pattern shape of the photoresist can be further improved. Further, the method for purifying the resin (A1) may, for example, be a chemical purification method such as water washing or liquid-liquid extraction, or a combination of chemical purification methods such as ultrafiltration or centrifugation and the like. In the present invention, the resin (A1) may be used alone or in combination of two or more. Further, the sensitive radiation linear resin composition (I) of the present invention may contain, as the resin component (A), another resin (A2) in addition to the above resin (A1). The other resin (A2) includes, for example, [1] the repeating unit (a2) and the repeating unit (a3), [2] the repeating unit (a2) and the repeating unit (a3) and the repeating unit ( A4), -39- 201013309 A resin composed of at least one of the above repeating unit (a5) and the aforementioned "other repeating unit". The other resin (A2) may be used singly or in combination of two or more. In the present invention, the content of the resin (A1) is characterized by more than 50% by mass when the resin component (A) contained in the radiation-sensitive linear resin composition (I) of the present invention is 1% by mass in total. The case where the resin (A1) is 100% by mass]. That is, the content of the other resin (A2) is 0 to 5 % by mass. In particular, the content of the resin (A1) is preferably 100% by mass or more, more preferably 5 5 to 100% by mass. When the content of the resin (A1) exceeds 50% by mass, the swelling at the time of development can be suppressed by the influence of the repeating unit (a1) contained, and it is expected that the pattern is deteriorated (pattern collapse). . Further, in the liquid immersion process, the resin has a moderate water repellency because it contains a repeating unit (al), and can also be used for a liquid immersion process in the case of a non-protective film. When the amount is 50% by mass or less, the above effects may not be obtained. 0 < (B) Sensitive radiation linear acid generator> The (B) radiation sensitive linear acid generator of the present invention "hereinafter also referred to as acid generator (B)" is an acid produced by exposure, by exposure The action of the generated acid 'dissociates the acid-dissociable group of the above-mentioned repeating unit (al) or (a2) present in the resin component (the protective group is detached), and as a result, the exposed portion of the photoresist film is in the alkali image It is easily soluble in the liquid and has a role in forming a positive resist pattern. The acid generator (B) preferably contains a compound represented by the following general formula (4): -40 to 201013309 (hereinafter referred to as "acid generator i"). 【化1 6】 R15

(4) k k in the above general formula (4) is an integer of 〇~2. Further, R15 represents a hydrogen atom, a fluorine atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, or carbon. A linear or branched alkoxycarbonyl group of 2 to 11 is used. Further, R16 represents a linear or branched alkyl group having 1 to 1 carbon atom, a linear or branched alkoxy group having 1 to 1 carbon number, or a straight carbon number of 1 to 1 Å. A chain, branched, or cyclic alkanesulfonyl group. r is an integer from 0 to 10. φ Further, R17 independently of each other represents a linear or branched alkyl group having 1 to 10 carbon atoms, a phenyl group which may be substituted, or a naphthyl group which may be substituted, or a carbon in which two R17 are bonded to each other. The number 2 to 10 of the 2 valence group. This divalent group can be substituted. Further, the X system is represented by the formula: R18CnF2nS〇3· or R18S〇3_ (wherein R18 represents a fluorine atom or a hydroxyl group having 1 to 12 carbon atoms which may be substituted, and an integer of 11 systems 1 to 1〇) An anion, or the following general formula (5-1) or (5-2) represents an anion. -41 - 201013309 【化1 7】

(δ-1)

In the above general formula (5_1) or (5·2), R19 independently represents a linear or branched alkyl group containing a fluorine atom, or a carbon in which two R19 are bonded to each other. A divalent organic group containing a fluorine atom in the range of 2 to 10. This divalent organic group may have a substituent. In the general formula (4), a linear or branched alkyl group having 1 to 10 carbon atoms of R15, R16 and R17, for example, a methyl group, an ethyl group, a propyl group, an i-propyl group or a η-butyl group. Base, 2-methylpropyl, 1-methylpropyl, t-butyl, n-pentyl, neopentyl 'n-hexyl, η-heptyl, η-octyl, 2-ethylhexyl, Η-fluorenyl, η-fluorenyl and the like. Among these alkyl groups, a methyl group, an ethyl group, an η-butyl group, a t-butyl group and the like are preferable. a linear or branched alkoxy group having 1 to 1 carbon atoms of R15 and R16, for example, a methoxy group, an ethoxy group, a η-propoxy group, an i-propoxy group, and an η-butoxy group. , 2-methylpropoxy, 1-methylpropoxy ' t-butoxy, η-pentyloxy, neopentyloxy, η-hexyloxy, η-heptyloxy, η-octyloxy Base, 2-ethylhexyloxy, η-methoxyl, η-decyloxy, and the like. Among these alkoxy groups, methoxy group, ethoxy group, η-propoxy group, η-butoxy group and the like are preferable. Further, a linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms of R15 is exemplified by a methoxycarbonyl group, an ethoxycarbonyl group, an η-propoxycarbonyl group, and an i-iso-42-201013309 Oxycarbonyl, η·butoxycarbonyl, 2-methylpropoxy male propoxycarbonyl, t-butoxycarbonyl, η-pentyloxycarbonyl, benzyl, η-hexyloxycarbonyl, η-g The oxycarbonyl group, the η-octyloxyhexyloxycarbonyl group, the η-methoxycarbonyl group, and the η-decyloxycarbonyloxycarbonyl group are preferably a methoxycarbonyl group, an ethoxycarbonyl group, a group or the like. Further, the linear or branched φ alkanesulfonyl group having a carbon number of 1 to 1 Å of R16 is, for example, a methanesulfonyl group, an ethanesulfonyl fluorenyl group, an η-butanesulfonyl group, t- Butanesulfonyl, η-pentanepentanesulfonyl, η-hexanesulfonyl, η-heptanesulfonyl, benzyl, 2-ethylhexylsulfonyl, η-decanesulfonate Base, η-fluorene cyclopentanesulfonyl, cyclohexanesulfonyl and the like. These alkane sulfonates are preferably methanesulfonyl, ethanesulfonyl, η-propanesulfonyl fluorenyl, cyclopentanesulfonyl, cyclohexanesulfonyl and the like. Further, r in the above general formula (4) is an integer φ 0 to 2 of 0 to 10. In the general formula (4), a phenyl group which may be substituted for R17, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,3 -di 2,4-dimethylphenyl group, a 2,5-dimethyl group Phenylphenyl, 2,6-dimethyldimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenylphenyl, 4-t-butylphenyl, 4 a cyclohexylphenyl group, a 4-fluorobenzene or a linear, branched or cyclic alkyl group having a carbon number of 1 to 1 fluorene; such a phenyl or alkyl substituted phenyl group having a hydroxyl group, a carboxyl group, Alkoxy groups, a homesteads, a home base, an alkoxy group, a 1-methyl neopentyloxycarbonylcarbonyl group, a 2-ethyl group, and the like. Such alkane η·propoxycarbonyl, or cyclic: η-propane sulfonyl sulfhydryl, new η _ _ _ _ _ 院 扩 扩 、 、 、 、 、 、 、 、 、 、 中Preferably, it is a phenyl group-substituted phenylcyano group, a nitrocarbonyloxy group, etc. having a phenylmethylphenyl group, a fluorenylphenyl group, a 3,4-yl group, a 4-ethyl group, etc. -43- 201013309 One or more substituted groups or the like. In the substituent of the phenyl group and the alkyl-substituted phenyl group, the aforementioned alkoxy group is, for example, a methoxy group, an ethoxy group, a η-propoxy group, a fluorenyl-propoxy group, a η-butoxy group, or a 2-methyl group. a linear, branched, or cyclic alkoxy group having a carbon number of 1 to 20, such as a propoxy group, a 1-methylpropoxy group, a t-butoxy group, a cyclopentyloxy group, or a cyclohexyloxy group. Base. Further, the above alkoxyalkyl group is, for example, a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, a 2-methoxyethyl group, a 1-ethoxyethyl group, a 2-ethyl group. a linear, branched or cyclic alkoxyalkyl group having a carbon number of 2 to 2 1 such as an oxyethyl group. Further, the above alkoxycarbonyl group has, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a η-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, a 2-methylpropoxycarbonyl group, and 1 a linear, branched or cyclic alkoxycarbonyl group having 2 to 21 carbon atoms such as a methylpropoxycarbonyl group, a t-butoxycarbonyl group, a cyclopentyloxycarbonyl group or a cyclohexyloxycarbonyl group. The above alkoxycarbonyloxy group is, for example, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an η-propoxycarbonyloxy group, an i-propoxycarbonyloxy group or an n-butoxycarbonyloxy group. a linear, branched or cyclic alkoxycarbonyloxy group having a carbon number of 2 to 2, such as a butyloxycarbonyloxy group, a cyclopentyloxycarbonyloxy group or a cyclohexyloxycarbonyloxy group; A phenyl group which may be substituted with Ri 6 in the general formula (4), preferably a phenyl group, a 4-cyclohexylphenyl group, a 4-t-butylphenyl group, a 4-methoxyphenyl group. , 4-t-butoxyphenyl and the like. A naphthyl group which may be substituted by R17, for example, 1-naphthyl group, 2-methyl-1-naphthalene-44-201013309 group, 3-methyl-1-naphthyl group, 4-methyl-1- 1-naphthyl group, 5-methyl-1-naphthyl, 6-methyl-1-naphthyl, 7-methyl-1-naphthyl, 8-methyl-1-naphthyl, 2,3-dimethyl-1- Naphthyl, 2,4-dimethylcaffeyl, 2,5-dimethyl-1_naphthyl, 2,6-dimethyl-1- 1 -naphthyl, 2,7-dimethyl.:!- Naphthyl, 2,8-dimethyl-1-naphthyl, 3,4-dimethyl-1-naphthyl, 3,5-dimethyl-1-naphthyl, 3,6·dimethylnaphthalene , 3,7-dimethyl-1-naphthyl, 3,8-dimethyl-1-naphthyl, 4,5-dimethyl-1-naphthyl, 5,8-dimethyl-1 -naphthyl, 4-ethyl-1-naphthyl, 2-naphthyl, 1-0 methyl-2-naphthyl, 3-methyl-2-naphthyl, .4-methyl-2-naphthyl a naphthyl group or a naphthyl group having a linear 'branched or branched chain of 1 to 10 carbon atoms; or a naphthyl group or an alkyl group substituted with a naphthyl group, having a hydroxyl group, a carboxyl group or a cyano group And one or more substituted groups of at least one of a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxyfluorenyl group, and an alkoxycarbonyloxy group. The alkoxy group, alkoxyalkyl group, alkoxycarbonyl group and alkoxycarbonyloxy group of the above substituent are, for example, those exemplified above for the phenyl group and the alkyl-substituted phenyl group. R17 of the general formula (4) The naphthyl group which may be substituted, for example, an anthracene-naphthyl group, a 1-(4-methoxynaphthalene) group, an i-C4·ethoxynaphthalene group, a 1-(4-n-propoxynaphthalene) group, -(4-n-butoxynaphthalenyl), 2-(7-methoxynaphthalenyl), 2-(7-ethoxycaline), 2-(7-n-propoxynaphthalenyl) , 2-(7-n-butoxynaphthalenyl) group, and the like. Two R17 groups are bonded to each other to form a carbon number of 2 to 1 fluorene. Preferably, the sulfur atom in the general formula (4) forms a 5-member or 6-membered ring together, and particularly preferably a member ring (ie, tetrahydrogen). The base of the thiophene ring). Further, examples of the substituent of the above-mentioned divalent group include a hydroxyl group, a carboxyl group, an aryl group, a nitro group, an alkoxy group, and an alkoxy group exemplified for the substituent of the above benzene-45 - 201013309 group and an alkyl-substituted phenyl group. An alkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group or the like. R17 of the general formula (4) is preferably a methyl group, an ethyl group, a phenyl group, a 4 methoxyphenyl group, a 1-naphthyl group, or two R17 groups bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom. The 2 price base and so on. The X_ system of the general formula (4) represents R18CnF2nS03·, R18S03· or the above general formula (5·1) or (5-2) represents an anion. X· is a perfluoroalkylene group of -CnF2n-based carbon number η when R18CnF2nS03· φ, but this may be linear or branched. Wherein η is preferably 1, 2, 4 or 8. The hydrocarbon group having 1 to 12 carbon atoms which may be substituted by R18, preferably an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or a bridged aliphatic hydrocarbon group. Specific examples are methyl, ethyl, η-propyl, i-propyl, η-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, η-pentyl, neopentyl Base, η-hexyl, cyclohexyl, η-heptyl, η-octyl, 2-ethylhexyl, η-fluorenyl, η-fluorenyl, norbornyl, norbornylmethyl, hydroxynorbornyl, Adamantane thiol and the like. When X. is an anion represented by the above general formula (5-1) or (5-2), R19 may be a linear or branched alkyl group containing a fluorine atom independently of carbon number 10, or Two divalent organic groups containing a fluorine atom having 2 to 10 carbon atoms formed by bonding R19 to each other, and the divalent organic group may have a substituent. In the general formula (5-1) or (5-2), when R19 is a linear or branched alkyl group having a carbon number of 1 to 1 Å, for example, trifluoromethyl, pentafluoroethyl or heptafluoro Propyl, nonafluorobutyl, dodecafluoropentyl, perfluorooctyl and the like. -46 - 201013309 And 'R19 is a divalent organic group having a carbon number of 2 to 10', for example, tetrafluoroethylene, hexafluoropropyl, octafluorobutyl, decafluoropentyl, eleven fluoride Heji and so on. Therefore, preferred anions X in the above general formula (4) are, for example, a trifluoromethanesulfonate anion, a perfluoroη-butanesulfonate anion, a perfluoroη-octanesulfonate anion, a 2-bicyclic ring. [2.2.1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate anion, 2-bicyclo[2.2.1]hept-2-yl-1,1-difluoroethane φ sulfonate anion 'anion such as the following formula (6-1) to (6-7) 〇 [化1 8] 兹23⁄4办& (6·1) (6-2) (6-3 (6-4) (6-5) (6^) (6-7) Further, the preferred example of general formula (4) is triphenylsulfonium trifluoromethane, acid salt, tri-t-butyl Diphenyl fluorene triflate, 4-cyclohexyl phenyl-diphenyl mirror trifluoromethane sulfonate, 4-methanesulfonyl phenyl-diphenyl fluorene difluoride , 1-(3,5-dimethyl-4-phenylphenyl)tetrahydrothiophene trifluoromethanesulfonate, butoxynaphthyl)tetrahydrothiophene trifluoromethanesulfonate, triphenyl锜Perfluoro-η-butane sulfonate, tri-t-butylphenylhydrazine perfluoro-η-butane sulfonate, 4-cyclohexylphenyl-diphenylfluorene perfluoro-η-butane Sulfonate, 4-ayuan diphenyl phenyl mirror Fluorine-n-butyl compound, acid salt, 1-47-201013309 (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophene gun perfluoro-η-butane sulfonate, 1- ( 4 -η-butoxynaphthyl)tetrahydrothiophene perfluoro-η-butane sulfonate, triphenylsulfonium perfluoro-η-octane sulfonate, tri-t-butylphenylhydrazine perfluoro -n-octane sulfonate, 4-cyclohexylphenyl-diphenylfluorene perfluoro-η-octane sulfonate, 4-methanesulfonylphenyldiphenylphosphonium perfluoro- η-octane Alkane sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene iron perfluoro-η-octane sulfonate, 1-(4-η-butoxynaphthyl) Tetrahydrothiophene perfluoro-η-octane sulfonate, triphenylsulfonium 2-(bicyclo[2.2.1]hept-2'-yl)-1,1,2,2-tetrafluoroethanesulfonic acid Salt, tris-t-butylphenyl hydrazine 2-(bicyclo[2.2.1]heptan-2'-yl)- 1.1.2.2-tetrafluoroethane sulfonate, 4-cyclohexylphenyl-diphenyl锍2-(bicyclo[2.2.1]hept-2'-yl)-1,1,2,2-tetrafluoroethane sulfonate, 4-methanesulfonylphenyl-diphenyl mirror 2-( Bicyclo[2.2.1]hept-2'-yl)-1,1,2,2-tetrafluoroethanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene铛2- (bicyclo[2.2.1]g-2'- -1,1,2,2-tetrafluoroethanesulfonate, 1-(4-η-butoxynaphthyl)tetrahydrothiophene gun 2-(bicyclo[2.2.1]hept-2'-yl )- 1.1.2.2- Tetrafluoroethane sulfonate, triphenylsulfonium 2-(bicyclo[2.2.1]hept-2'-yl)-1,1-difluoroethanesulfonate, tri-t -butylphenylhydrazine 2-(bicyclo[2.2.1]hept-2'-yl)-1,1-difluoroethanesulfonate, 4-cyclohexylphenyl-diphenylfluorene 2-(bicyclic [2.2.1] Hept-2'-yl)-1,1-difluoroethanesulfonate, 4-methanesulfonylphenyl-diphenylfluorene 2-(bicyclo[2.2.1]hept-2 '-yl)-1,1-difluoroethanesulfonate, ΙΟ)-dimethyl-4-hydroxyphenyl) tetrahydrothiophene 2-(bicyclo[2.2.1]hept-2'-yl) -1,1-difluoroethanesulfonate, 1-(4--η-butoxynaphthyl)tetrahydrothiophene 2-(bicyclo[2·2·1]hept-2'-yl)- 1,1-difluoroethanesulfonate-48-201013309, a compound represented by the following formulas B1 to B15, and the like. [化1 9]

-49- 201013309 【化2 2】

B7

[化2 3]

[化2 4] f3cn

F2C Ν· η 〇< cf2 CF,

F2Cn f3c CF, B11 B12 -50- 201013309 【化2 5】

B13

Further, in the present invention, the acid generator 1 may be used singly or in combination of two or more. In addition, a sensitive radiation linear acid generator other than the aforementioned acid generator 1 (hereinafter referred to as "other acid generator") can be used as the acid generator (B), for example, a gun salt compound, a halogen-containing compound, a diazoketone a compound, a maple compound, a sulfonic acid compound, or the like. Such other acid generators are, for example, those described below. (gun salt compound) The above key salt compound is, for example, an iodine salt, a sulfonium salt, a money salt, a diazo gun salt, a pyridine gun salt or the like. Specific examples of the gun salt compound are diphenyl iodide trifluoromethanesulfonate, diphenyl iodide pentafluoro-η-butane sulfonate, diphenyl iodine perfluoro-n-octane sulfonate. , diphenyl iodide 2 · bicyclo [2_2.1] hept-2-yl-1,1,2,2-tetrafluoroethane sulfonate, bis(4-t-butylphenyl) iodine gun three Fluoromethanesulfonate, bis(4-t-butylphenyl) iodine gun nonafluoro-n-butane sulfonate, bis(4-t-butyl-51 - 201013309 phenyl) iodine perfluoro- Η-octane sulfonate, bis(4-t-butylphenyl) iodine gun 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethane sulfonate Cyclohexyl. 2_ oxocyclohexylmethylsulfonium trifluoromethanesulfonate, dicyclohexyl-2-oxocyclohexylfluorene trifluoromethanesulfonate, 2-oxocyclohexyldimethylphosphonium trifluoride Methanesulfonate and the like. (Halogen-containing compound) The halogen-containing compound may, for example, be a halogenated alkyl group-containing hydrocarbon compound or a halogenated alkyl group-containing heterocyclic compound. Specific examples of the halogen-containing compound are phenylbis(trichloromethyl)-s-triazine, 4-methoxyphenylbis(trichloromethyl)-s-triazine, 1-naphthylbis(trichloro) (Trichloromethyl)-s-triazine derivatives such as methyl)-s-triazine, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, and the like. (diazonone compound) The diazoketone compound may, for example, be a 1,3-diketo-2-diazo compound, a diazobenzene compound or a diazonaphthoquinone compound. Specific examples of the diazoketone compound are 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 2,3,4,4' - 1,2-naphthoquinonediazide-4-sulfonate or 1,2-naphthoquinonediazide-5-sulfonate of tetrahydroxybenzophenone, 1,1,1-tri 1,2-naphthoquinonediazide-4-sulfonate or 1,2-naphthoquinonediazide-5-sulfonate of 4-hydroxyphenyl)ethane. (砸 compound) -52- 201013309 The aforementioned milled compound is, for example, β-keto maple, β-sulfonyl mill, or the like (X-diazo compound, etc.) A specific example of the maple compound is 4-triphenylhydrazine. Methyl mill, cresyl phenyl hydrazine methyl hydrazine, bis(phenylsulfonyl) methane, etc. (sulfonic acid compound) The above sulfonic acid compound is, for example, an alkyl sulfonate or an alkyl sulfonate y a haloalkyl sulfonate, an aryl sulfonate, an imide sulfonate, etc. Specific examples of the sulfonic acid compound are benzoin tosylate, pyrogallol tris(trifluoromethanesulfonate), Nitrobenzyl-9,10-diethoxyindole-2-sulfonate, trifluoromethanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide, nine Fluoro-η-butanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide, perfluoro-η-octanesulfonylbicyclo[2.2.1]hept-5 -ene-2,3-dicarbodiimide, 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarbodiimide, Ν-(trifluoromethanesulfonyloxy #) succinimide, Ν-(nonafluoro-η-butane sulfonyloxy) amber ylide , Ν-(perfluoro- Η-octanesulfonyloxy) succinimide, Ν-(2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy)arene Imine, octadecyltrifluoromethanesulfonate 1,8-naphthalene dicarboxylate, decyl iodide, 9-naphthalene dicarboxylate, 1,8-naphthalene dicarboxylate Among the other acid generators, diphenyl iodine trifluoromethanesulfonate and diphenyl iodine pentafluoro-n-butyl are preferred. Alkane sulfonate, diphenyl iodide perfluoro-η-octane sulfonate, diphenyl iodine 2-cyclo[2.2.1]hept-2-yl-1,1,2,2-53 - 201013309 Tetrafluoroethanesulfonate, bis(4-t.butylphenyl)iron iodide trifluoromethanesulfonate, bis(4-1-butylphenyl)iodonium nonafluoro-η-butane Sulfonic acid ester, bis(4-t-butylphenyl) iodine perfluoro-η-octane sulfonate, bis(4-t-butylphenyl) iodine 2-bicyclo[2.2.1] -2-yl-1,1,2,2-tetrafluoroethane sulfonate, cyclohexyl-2-oxocyclohexylmethylsulfonate, dicyclohexyl. 2-oxo ring Hexyltrifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate Indenylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide 0, nonafluoro-η-butanesulfonylbicyclo[2.2.1]hept-5-ene-2,3 - dicarbodiimide, perfluoro-η-octanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide, 2-bicyclo[2.2,1]hept-2 -yl-1,1,2,2-tetrafluoroethanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide, fluorene-(trifluoromethanesulfonyloxy) Amber imine, Ν-(nonafluoro-η-butanesulfonyloxy) succinimide, hydrazine-(perfluoro-n-octanesulfonyloxy) succinimide, hydrazine - (2 -bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) succinimide, 1,8-naphthalene dicarboxylic acid quinone imine trifluoromethane sulfonate Acid esters, etc.其他 The above-mentioned other acid generators may be used singly or in combination of two or more. In the present invention, the total amount of the acid generator 1 and other acid generators is from the viewpoint of ensuring sensitivity and development as a photoresist. It is usually 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of the resin component (Α). In this case, when the total amount used is less than 0.1 part by mass, the sensitivity and developability tend to be lowered. On the other hand, when the total amount used is more than 2 parts by mass, the transparency to the radiation is lowered, and it may be difficult to obtain a rectangular photoresist pattern of -54 to 201013309. In addition, the ratio of use of the other acid generator is 10% by mass to the total of the acid generator 1 and the other acid generator, and is usually 8% by mass or less, preferably 60% by mass or less. <Solvent (C) > The radiation-sensitive linear resin composition (I) of the present invention is generally used, and the total solid content of Φ is usually from 1 to 50% by mass, preferably from 1 to 25% by mass, after dissolution in a solvent. For example, it is filtered by a filter having a pore size of about 2 μm, and is prepared in the form of a composition solution. The solvent (C) is, for example, 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentyl a linear or branched ketone such as a ketone, 3,3-dimethyl-2-butanone, 2-heptanone or 2-octanone; cyclohexanone, 3-methylcyclopentanone, cyclohexanone, a cyclic ketone such as 2-methylcyclohexanone, 2,6-dimethylcyclohexanone or isophorone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-η-propyl Ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-η-butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol Propylene glycol monoalkyl ether acetates such as mono-t-butyl ether acetate; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, η-propyl 2-hydroxypropionate, 2-hydroxypropionic acid 2-hydroxyl of i-propyl ester, η-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate, t-butyl 2-hydroxypropionate Alkyl propionate; 3-methoxylpropionate methyl ester, 3-methoxypropionate ethyl ester, 3-ethoxypropionate methyl ester, 3-ethoxypropionate ethyl ester, etc. 3-alkoxy Alkyl propionate; -55- 20101330 9 η-propanol, i-propanol ' η-butanol, t-butanol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-η-propyl ether, ethylene Alcohol mono-η-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-η-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol single Methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-η-propyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-η-propyl ether, toluene, xylene, Ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3 -methyl-3- φ methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, acetic acid Ester, η-propyl acetate, η-butyl acetate, methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, Ν-methylpyrrolidone, hydrazine, hydrazine-dimethyl醯amine 'Ν, Ν-dimethylacetamide, benzyl ether, di-η-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Acid, citric acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate Wait. ❹ Among these, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, 2-hydroxypropionic acid alkyl esters, and 3-alkoxypropionic acid alkyl esters are preferred. , γ-butyrolactone and the like. These solvents (C) may be used alone or in combination of two or more. <Nitrogen-containing compound> The radiation sensitive linear resin composition (I) of the present invention may contain a nitrogen-containing compound -56-201013309 in addition to the above-mentioned resin component (Α), acid generator (Β), and solvent (C). This nitrogen-containing compound controls a diffusion phenomenon in which an acid generated from an acid generator diffuses into a photoresist film due to exposure, and has a function of suppressing a poor chemical reaction in a non-exposed region (acid diffusion controlling agent). By incorporating such an acid diffusion controlling agent, the storage stability of the resulting radiation sensitive linear resin composition can be improved. Further, the resolution of the photoresist can be further improved, and the line width variation of the resist pattern due to the change in the standing time (PED) from the exposure to the heat treatment after the exposure can be suppressed, and the process stability can be excellent. Composition. Examples of the nitrogen-containing compound include a tertiary amine compound, another amine compound, a guanamine group-containing compound, a urea compound, and other nitrogen-containing heterocyclic compounds. The tertiary amine compound is preferably a mono(cyclo)alkylamine such as η-hexylamine, n-heptylamine, cardinamine, η-decylamine, η-decylamine, cyclohexylamine or the like; di-n-butyl Amine, di-η-pentylamine, di-η-hexylamine, di-η-heptylamine, di-n-octylamine, Φ di-η-decylamine, di-η-decylamine, cyclohexylmethylamine, Dicyclohexylamine and other di(cyclo)amines, diethylamine, di-η-propylamine, di-η-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-g Amine, tri-η-octylamine, tri-n-decylamine, tri-n-decylamine, cyclohexyl-monomethylamine, methyldicyclohexyl 3 female, S cyclohexylamine, etc. , 2,2',2"-nitro-triethanol temple substituted amines; aniline, N-methylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4- Methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2,4,6-tri-t-butyl-N-methylaniline, N-phenyldiethanolamine, 2,6-diisopropylaniline, etc. • 57- 201013309 The other amine compounds mentioned above include, for example, ethylenediamine, n, n, n, n'-tetramethylethylenediamine, butanediamine, hexamethylenediamine, 4,4'-diamino 2 Methane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4,diaminodiphenylamine, 2,2.bis(4-amine Phenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane, 2-(4-Aminophenyl)-2-(4-hydroxyphenyl)propane, 1,4-bis[1-(4-aminophenyl)-1-methylethyl]benzene, 1, 3_bis[1-(4-aminophenyl)-1-methylethyl]benzene, bis(2-dimethylaminoethyl)ether, bis(2-diethylaminoethyl)ether , 1-(2-hydroxyethyl)-2.imidazolidinone, 2-quinoxaline, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, N,N,N ', N", N"-pentamethyldiethylenetriamine, etc. The aforementioned guanamine-containing compound ' is preferably, for example, Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi -η-decylamine, Nt-butoxycarbonyldi-n-decylamine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantanamine, Nt-butoxycarbonyl- 2-adamantamine, Nt-butoxycarbonyl-N-methyl-b-amantaneamine, (S)-(-)-1-(-t-butoxycarbonyl)-2- Methanol, (R)_(+) _1_(·Budoxy-yl)-2_Laoyuan Methanol, Nt-butoxycarbonyl-4-trans-based, N+butoxy-based Home, Nt-butoxy-ipylpiperazine, Nt-butoxydecylpiperazine, N,N-di-1-butoxycarbonyl-bumantanamine, N,N-di+butoxyl group N-methyl_1_adamantanamine, N-t_butoxycarbonyl-4,4'-diaminodiphenylmethane, N,N'-di-t-butoxycarbonylhexamethylenediamine, n ,n,n',n'-tetra-t-butoxycarbonylhexamethylenediamine, N,N,-di-t-butoxycarbonyl·1,7-diaminoheptane' N,N'· Dibutyloxycarbonyl-1,8-diaminooctane, N,N'-di-t-butoxycarbonyl-1,9,-201013309 Amino decane, hydrazine, Ν'-di-t -butoxycarbonyl-1,10-diaminodecane, N,N'-di-t-butoxycarbonyl-1,12-diaminododecane, anthracene, Ν'-di-t- Butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2 -N-butoxycarbonyl-containing amine-based compound such as phenylbenzimidazole, and formamide, N-methyl Formamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, acetamide, benzamide, pyrrolidone, N -methylpyrrolidone, N-ethinyl-1-adamantanamine, tris(2-hydroxyethyl) isocyanurate, and the like. The aforementioned urea compound is preferably, for example, urea, methyl urea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-two Phenylurea, tri-n-butylthiourea, and the like. The above other nitrogen-containing heterocyclic compound is preferably, for example, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2- Imidazoles such as methylimidazole, 1-benzyl-2-methyl-1-indole-imidazole; φ pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2 -phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinic acid decylamine, quinoline, 4-hydroxyquinoline, 8-hydroxyquinoline, Acridine, 2,2 ' : 6 ',2 ′-pyridines such as terpyridine; piperazines such as piperazine and (2-hydroxyethyl) piperazine, and pyrazine, pyrazole, pyridazine, Quinozaline, hydrazine, pyrrolidine, piperidine, piperidine ethanol, 3-piperidinyl-1,2-propanediol, morpholine, 4-methylmorpholine, 1 _(4-morpholine Ethyl alcohol, 4-ethionylmorpholine, 3-(N-morpholinyl)-12-propanediol, I,4-dimethylpiped, 1,4-diazabicyclo[2·2·2 ] octane, etc. -59- 201013309 The above nitrogen-containing compounds may be used alone or in combination of two or more. The amount of the acid diffusion controlling agent is more than 100 parts by mass, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the resin component (A). When the amount is 15 parts by mass, the sensitivity as a photoresist tends to decrease. When the amount of the acid diffusion controlling agent is less than 0.01 part by mass, the pattern shape or dimensional fidelity as a photoresist may be lowered due to process conditions. <Additive> In the radiation sensitive linear resin composition (I) of the present invention, various additives such as an alicyclic additive, a surfactant, a sensitizer, and the like may be blended as needed, and the aforementioned alicyclic additive system is further improved. a component that resists dry etching, pattern shape, adhesion to a substrate, etc. The alicyclic additive 'is, for example, 1 adamantanecarboxylic acid, 2-adamantane beta ketone, 1-adamantanecarboxylic acid t- Butyl ester, 1-adamantanic acid t-butoxycarbonyl methyl ester, 1-adamantanecarboxylic acid α-butyrolactone, 1,3-adamantane dicarboxylic acid di-t-butyl ester, and baudhamane acetic acid t- Butyl ester, 1-adamantanic acid t-butoxycarbonyl methyl ester, 1,3_adamantane diacetic acid Adamantane derivatives such as t-butyl ester and 2,5-dimethyl-2,5-di(adamantylcarbonyloxy)hexane: t-butyl deoxycholate and t-butyl deoxycholate Oxygen-based methyl acetonate, 2-ethoxyethyl deoxycholate, 2-cyclohexyloxyethyl deoxycholate, 3-oxocyclohexyl deoxycholate, tetrahydropyranyl deoxycholate, deoxycholate Deoxycholate such as valerolactone; lithocholic acid t_butyl-60-201013309 ester, t-butoxycarbonyl methyl lithate, 2-ethoxyethyl lithic acid, lithocholic acid 2- a choline ester such as cyclohexyloxyethyl ester, 3-oxocyclohexyl lithate, tetrahydropyran thioate, valeric acid glutarate; dimethyl adipate, hexane An alkyl carboxylate such as diethyl diester, dipropyl adipate, di-n-butyl adipate, di-t-butyl adipate, or 3-[2-hydroxy-2,2- Bis(trifluoromethyl)ethyl]tetracyclo[4.4.0.12'5.17 = 1Q]dodecane and the like. These alicyclic additives may be used alone or in combination of two or more. φ Further, the surfactant is a component which exhibits an effect of improving coatability, streaking, and developing properties. Such surfactants, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyethylene oxide oleyl ether, polyethylene oxide η-octyl phenyl ether, polyethylene oxide η-mercaptophenyl ether, polyethylene A nonionic surfactant such as an alcohol dilaurate or a polyethylene glycol distearate, and the following trade names: ΚΡ341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, and the same Ν. Rongshe Chemical Co., Ltd.), EFtop EF301, #EF3 03, EF3 52 (made by TOHKEM PRΟDUCTS Co., Ltd.), Megafac F171, F173 (made by Dainippon Ink Chemical Industry Co., Ltd.), Florad FC430, and FC431 (Sumitomo 3M AG), Asahiguard AG710, Surflon S-3 82 > with SC-101' with SC-102, with SC-103, with SC-104, with SC-105, with SC-106 (made by Asahi Glass Co., Ltd. )Wait. These surfactants may be used alone or in combination of two or more. Further, the aforementioned sensitizer is a linear resin composition which exhibits energy for absorbing radiation and transmits its energy to the acid generator (B), thereby increasing the amount of acid generated, -61 - 201013309 The effect of the apparent sensitivity. Such sensitizers are, for example, carbazoles, acetophenones, benzophenones, naphthalenes, phenols, dithizone, eosin, rose bengal, anthraquinones, anthraquinones, phenothiazines and the like. These sensitizers may be used alone or in combination of two or more. Further, by blending a dye or a pigment, the latent image of the exposed portion can be visualized, the effect of blooming at the time of exposure can be alleviated, and the adhesion to the substrate can be improved by blending the auxiliary agent. Further, the additives other than the above include, for example, an alkali-soluble resin, a low-molecular alkali solubility control agent having a Q-protecting group having an acid dissociation property, an anti-fog stabilizer, a storage stabilizer, an antifoaming agent, and the like. [2] Sensitive radiation linear resin composition (II) The other radiation sensitive linear resin composition of the present invention (hereinafter also referred to as "sensitive radiation linear resin composition (Π)") contains a wavelength of 1 93 nm. In the state in which the refractive index is higher than that of the liquid immersion exposure liquid, the light is formed by irradiating the resist film formed on the substrate with a radiation pattern and exposing the liquid to the n-light step pattern. A sensitive radiation linear resin composition for a barrier film. The above-mentioned sensitive radiation linear resin composition (Π) is defined by the following formula (i). Preferably, K1 = F1/F 2 (i) is satisfied. [In the formula (i), F1 represents the most photosensitive film produced by the following conditions of surface element analysis and calculation of -62-201013309. Fluorine content near the surface (atom%). F2 is a fluorine content (atom%) in the vicinity of 20% of the film thickness of the photoresist film measured and measured by the following surface element analysis (production condition of the photoresist film): linearity of the sensitive radiation The resin composition was spin-coated on a substrate, and baked at 100 ° C for 60 seconds to prepare a photoresist film 〇 φ (surface elemental analysis) having a thickness of about 120 nm (particularly 80 to 160 nm, further 90 to 150 nm). The X-ray was irradiated to the photoresist film using a photoelectron spectroscope, and the amount of secondary electrons generated was measured, and the amount of fluorine atoms in the photoresist film was measured. The F! in the above formula (i) indicates the fluorine content (atom%) in the vicinity of the outermost surface of the resist film produced by the above-described surface conditions by the surface element analysis and calculation. "Near-surface" refers to a portion from the most surface side of the photoresist (the opposite side of the substrate contact surface) to within 7% of the film thickness (especially within 5%, further within 3%). Φ The F2 is a fluorine content (atom%) in the vicinity of 20% of the film thickness of the photoresist film produced by the above-described production conditions by the surface element analysis. "20% vicinity" means the range from the most surface side of the photoresist (the opposite side of the substrate contact surface) to the film thickness of 10-30% (especially in the range of 13 to 27%, further 15 to 25) The part of the range of %). In addition to the foregoing. It is preferably 1 $2 for those who meet ISKdS. When the Ki satisfies 1 $5, the fluorine content in the region of the thickness side of the photoresist is uniform in the thickness direction, and the fluorine in the film is at a lower rate of -63-201013309. In addition, when the temperature of the film is less than 1, the water repellency of the photoresist film tends to be poor. and. When it exceeds 5, there is a tendency that a good pattern shape cannot be obtained. Further, there is a tendency that defects such as development defects cannot be sufficiently controlled. In this way, when the linear resin composition satisfying the sensitivity of the guest is used, it is possible to obtain a photoresist having a high uniformity in the composition in the film thickness direction, and to obtain a liquid immersion exposure for water or the like which is in contact with the liquid immersion exposure. Since the amount of the liquid eluted matter is small and the solubility of the exposed portion to the developing liquid is increased, the development defect can be sufficiently suppressed. Moreover, the unevenness of the shape of the pattern can be improved. Because it has excellent water repellency and has a high receding contact angle of @, it is not necessary to form a protective film on the photoresist film, which is suitable for the immersion exposure process for forming a resist pattern. The above-mentioned sensitive radiation linear resin composition contains (A ') resin component, (B) a radiation sensitive linear acid generator, and (C) a solvent. The (B) radiation sensitive linear acid generator and the (C) solvent in the sensitive radiation linear resin composition (II) can directly use the acid generator (B) in the above-mentioned sensitive radiation linear resin composition (I) and Description of solvent (C).

(A') Resin component> The resin component (hereinafter also referred to as "resin component (A ')")) contains a repeating unit (al) having a fluorine atom and an acid dissociable group in the side chain. An acid-dissociable group-containing resin (A1). The acid-dissociable group-containing resin (A 1 ) can be directly used as the description of the resin (A1 ) in the above-mentioned radiation-sensitive linear resin composition (Ϊ). The sensitized radiation linear resin composition (A) of the present invention may contain, as the resin component (A), the other of the aforementioned sensitized radiation-64-201013309 resin composition (I) in addition to the above-mentioned resin (A1). Resin (A2). The content of the resin (A1) is preferably 50% by mass or more, more preferably 50% by mass, more preferably 50% by mass, based on 100% by mass of the total of the resin component (A') contained in the radiation sensitive linear resin composition (Π) of the present invention. ~100% by mass, more preferably 5 5~1 0 0% by mass. When the content of the resin (A1) exceeds 50% by mass, the swelling at the time of development can be suppressed by the influence of the repeating unit (a1) contained, and a pattern of a good shape 〇 can be obtained. Further, the resin (A1) has a moderate water repellency because it contains a repeating unit (al), and can also be used for a liquid immersion process without a protective film. When the content is 50% by mass or less, the above effects may not be obtained. Further, the sensitive radiation linear resin composition (Π) may contain, in addition to the resin component (A'), the acid generator (B) and the solvent (C), the content of the sensitive radiation linear resin composition (I). Nitrogen compound or additive [3] receding contact angle. Further, in the sensitive radiation linear resin compositions (I) and (II) of the present invention, the photoresist film formed by coating the resin composition on the substrate is repelled by water. The contact angle is preferably 68 degrees or more, more preferably 70 degrees or more. After the exit angle is less than 68 degrees, the water removal during high-speed scanning exposure is poor, and water mark defects may occur. In the present specification, the "retracted contact angle" means a liquid on a substrate on which a resist film of the resin composition of the present invention is formed, and water droplets on the substrate are sucked at a rate of 10 pL/min after water is dropped by 25 μM. The contact angle of the face to the substrate. -65-201013309 The measurement was carried out using "DSA-10" manufactured by KRUS Co., Ltd. as shown in the examples below. [4] Polymer The polymer of the present invention is represented by a repeating unit represented by the above general formula (1) and a repeating unit having a lactone skeleton. This polymer can be suitably used as the resin component in the above-mentioned liquid immersion exposure sensitive resin linear resin compositions (I) and (II). Further, the repeating unit represented by the general formula (1) and the repeating unit having a lactone skeleton can be directly applied to the repeating unit represented by the general formula (1) in the above-mentioned "resin (A1)", and the repeat having the lactone skeleton. Description of the unit (repeating unit (a3)). The polymer may contain a repeating unit (a2) in the above-mentioned resin (A1), a repeating unit containing an alicyclic compound, a repeating unit derived from an aromatic compound, and the like. [5] Photoresist film The sensitive radiation linear resin compositions (I) and (II) of the present invention can be used in a state in which a liquid for immersion exposure having a refractive index higher than that of air at a wavelength of 193 nm is used. The photoresist film used in the method for forming a photoresist pattern in which the photoresist film formed on the substrate is irradiated with radiation and exposed to a liquid immersion exposure step. The photoresist film is one of κ 2 defined by the following formula (Π). -66-201013309 K2 = F3/F4 (ii) In the formula (ii), F3 represents the fluorine content (atom%) in the vicinity of the outermost surface of the photoresist film measured and calculated by the following surface element analysis. F4 is a fluorine content (atom%) in the vicinity of 20% of the film thickness of the photoresist film measured and calculated by the following surface element analysis] φ (surface element analysis): used for the photoresist film The photoelectron spectroscope irradiates X-rays, measures the amount of secondary electrons generated, and measures the amount of distribution of fluorine atoms in the photoresist film. F3 in the above formula (ii) represents the fluorine content (atom%) in the vicinity of the outermost surface measured and calculated by the surface element analysis. "Approximate surface" means a portion from the surface side of one of the photoresists to within 7% of the film thickness (especially within 5%, further within 3%). Further, the above F2 means that the fluorine content (atom%) in the vicinity of 20% of the surface side of one of the surface of the photoresist of Φ is measured and calculated by the surface element analysis. "20% vicinity" means from the surface side of one of the aforementioned photoresists to the range of 10 to 30% of the initial film thickness (especially in the range of 13 to 27%, further I5 to 25%) The part within the range). The aforementioned K2 satisfies 1 g k2 $5, preferably 1 S K2 S 3 , more preferably 1 SK2S2. When K2 satisfies 1 SK2S5, the fluorine content in the region on the surface side of the photoresist is uniform in the thickness direction, and the bias ratio of fluorine in the film is low. Therefore, the photoresist film has sufficient water repellency. A defect such as a development defect can be sufficiently suppressed, and a good pattern shape can be obtained at the same time. -67- 201013309 [6] Method of Forming Photoresist Pattern The sensitive radiation linear resin compositions (I) and (H) of the present invention can be used as, in particular, a chemical profile type photoresist. The chemical ruthenium type resist is obtained by exposing an acid generated by an acid generator to dissociate an acid dissociable group in a resin component (mainly a resin (A1)) to form a carboxyl group, and as a result, an exposure portion of the photoresist The solubility in the alkali developing solution is increased, and the exposed portion is dissolved and removed by the alkali developing solution to obtain a positive resist pattern. The method for forming a specific photoresist pattern includes, for example, (1) a step of forming a photoresist film on a substrate using a sensitive radiation linear resin composition (hereinafter also referred to as "step (1)")" (2) The step of performing the immersion exposure on the photoresist film (hereinafter also referred to as "step (2)"), and (3) the step of developing the photoresist film after liquid immersion exposure to form a photoresist pattern (hereinafter also referred to as "step") The method of "Step (3)"). The above step (1) is a resin composition solution obtained from the sensitive radiation linear resin composition (I) or (II) of the present invention, which is suitably coated by spin coating, cast coating, roll coating, or the like. The means is, for example, applied to a substrate such as a tantalum wafer or an aluminum-coated wafer to form a photoresist film. Specifically, the resist radiation linear resin composition solution is applied. After the obtained photoresist film has a predetermined film thickness, the solvent in the coating film is volatilized by prebaking (PB) to form a photoresist film. The thickness of the photoresist film is not particularly limited, and is preferably 10 to 5 000 nm, more preferably 10 to 2000 nm. The pre-baking heating condition is preferably 30-200 ° C, more preferably 50-150 ° C, depending on the composition of the sensitive radiation 'linear resin composition-68-201013309'. The above step (2) is a liquid immersion medium such as water, and the radiation is irradiated onto the photoresist film formed in the step (1) to expose the photoresist film to liquid immersion. When exposed, radiation is typically illuminated by a reticle having a defined pattern. The radiation is used in combination with the type of the acid generator, and visible light, ultraviolet light, far ultraviolet light, X-ray, charged particle beam, etc. are suitably selected. Among them, an ArF excimer laser (wavelength 丨93 nm) or KrF is preferable. #分子激光 (wavelength 248nm) represents the far ultraviolet light, especially the ArF excimer laser (wavelength 193nm). The exposure conditions such as the amount of exposure are appropriately selected in accordance with the blending composition of the sensitive radiation linear resin composition, the type of the additive, and the like. In the present invention, heat treatment (PEB) after exposure is preferred. By this PEB, the dissociation reaction of the acid dissociable group in the resin component can be smoothly performed. The heating condition of PEB is appropriately adjusted depending on the compounding composition of the linear composition of the radiation sensitive radiation, and is usually 30 to 200 ° C, preferably 50 to 170 ° C. In the present invention, in order to exhibit the maximum potential of the radiation-sensitive linear resin composition, for example, the substrate that can be used is disclosed in Japanese Patent Publication No. Hei 6-1-2452 (JP-A-59-93 44). An organic or inorganic antireflection film is formed in advance. In order to prevent the influence of the alkaline impurities and the like contained in the ambient atmosphere, for example, a protective film can be provided on the photoresist film as disclosed in Japanese Laid-Open Patent Publication No. Hei 5-188598. In addition, in order to prevent the liquid immersion exposure, it is possible to provide a liquid immersion protective film on the photoresist film, as disclosed in Japanese Laid-Open Patent Publication No. 2005-3523 84, for example. Also, these techniques can be used. Further, in the method of forming a photoresist pattern by liquid immersion exposure, the above protective film (upper film) may not be provided on the photoresist film, and only by using the sensitive radiation linear resin composition of the present invention. The photoresist film forms a photoresist pattern. When the photoresist pattern is formed by the photoresist film having no upper film, the film forming step of the protective film (upper film) can be omitted, and productivity can be expected. The above step (3) is the photoresist after the liquid immersion exposure. The film is developed to form a predetermined photoresist pattern. The developing solution used for the development is, for example, preferably sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, η-propylamine, diethylamine or di-n. · propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo-[5·4.0] An aqueous alkaline solution in which at least one of the basic compounds such as 7-undecene and 1,5-diazabicyclo-[4.3.0]-5-decene are dissolved. The concentration of the alkaline aqueous solution is usually 10% by mass or less. When the concentration of the alkaline water solution exceeds 10% by mass, the non-exposed portion may be dissolved in the developing liquid. Further, an organic solvent may be added to the developing solution composed of the alkaline aqueous solution. The organic solvent is, for example, a ketone such as acetone, methyl ethyl ketone, methyl i-butanone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone or 2,6-dimethylcyclohexanone; Methanol, ethanol, η-propanol, i-propanol, η-butanol, t-butanol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1,4-hexanedimethanol, etc. Alcohols; ethers such as tetrahydrofuran and dioxane; esters of ethyl acetate, η-butyl acetate, i-amyl acetate, etc.; aromatic hydrocarbons such as toluene and xylene, 70-201013309, or phenol , acetone acetone, dimethylformamide, and the like. These organic solvents may be used alone or in combination of two or more. The organic solvent is used in an amount of preferably 100 parts by volume or less based on 100 parts by volume of the aqueous alkaline solution. When the amount of the organic solvent used exceeds 100 parts by volume, the developability is lowered, and the development of the exposed portion is increased. Further, an appropriate amount of interfacial activity may be added to the developing solution formed of the alkaline aqueous solution. Agents, etc. After development by a developing solution composed of a hydrophobic aqueous solution, it is usually washed with water and then dried. [Embodiment] EXAMPLES Hereinafter, embodiments of the present invention will be described more specifically by way of examples. However, the invention is not limited at all by these embodiments. Here, the quality standard is based on the absence of special pre-declaration. Π]sensitive radiation linear resin composition (I) [1-1] Synthesis of resin Each measurement and evaluation in each of the following synthesis examples was carried out in the following manner. (1) Mw and Μη GPC column (2 G2000HXL, 1 G3 000HXL > 1 G4000HXL) made by Tosoh Co., Ltd., at a flow rate of 1.0 ml/min, elution solvent tetrahydrofuran, column temperature 4 (TC) Under the conditions of analysis, it was determined by monodisperse-71 - 201013309 polystyrene as the standard gel permeation chromatography (GPC). Moreover, the dispersion Mw/Mn system was calculated from the measurement results. (2) 13C -NMR analysis The 13C-NMR analysis of each resin was carried out using "JNM-EX270" manufactured by JEOL Ltd. (3) The amount of the low molecular weight component derived from the monomer was determined by using GL Sciences Intersil ODS-25pm column (4.6 mm). φ χ 250 nm), measured by a high-speed liquid chromatography (HPLC) under the conditions of a solvent of acrylonitrile/0.1% phosphoric acid solution at a flow rate of 1.0 ml/min. The ratio of the component amount (% by mass) is 1 for the resin as a whole. In the case of the mass %, the respective synthesis examples are described below. Each of the monomers for the synthesis of the resin component (A) [resin (A-1) to (A-1 1 )] is represented by the following formula (M-1)~ (M-10) indicated. 201013309 [Chem. 2 6

t>°-b °-fc

(Μ-δ) (M-1) (M-2)

(M-3) (M-4)

(M-7) (M-8)

(M-9) (M-1〇) <Synthesis of Polymer (Al)> The aforementioned monomer (M-1) 34, 61 邑 (5 〇 mol%), the aforementioned monomer (M-6) 28.82g (10% by mole) and the aforementioned monomer (m-5) 36.57g (40% mole%) are dissolved in 2·butanone 2〇〇g, and then added to dimethylazobisisobutyronitrile 3.38 g, modulating the monomer solution. Separately, a 500-neck three-necked flask containing x-butanone was charged with nitrogen gas for 3 minutes, and after flushing with nitrogen, the reaction vessel was heated to 80 ° C under stirring, using a dropping funnel. The aforementioned monomer solution prepared beforehand was added dropwise over 3 hours. The polymerization was carried out for 6 hours starting from the start of the dropping as the polymerization start time. After the completion of the polymerization, the polymerization solution was cooled to 30 ° C or lower by water cooling, and poured into 2000 g of methanol, and the precipitated white powder was filtered. The white powder after filtration was washed with a slurry of 400 g of methanol twice, filtered, and dried at 50 ° C for 17 hours to obtain a copolymer of -73-201013309 to a white powder (yield 66.3%). The polymer system had a Mw of 7500, Mw/Mn=1.35, and 13C-NMR analysis. The content of each repeating unit derived from the monomers (Μ·1), (Μ-6), and (Μ-5) was 47.2. : 7.5 : 45.3 (mole %) copolymer. This polymer is used as a resin (Α·1). Further, the content of the low molecular weight component derived from each of the monomers in the resin (Α-1) is 100% by mass based on the polymer. When it is less than 0.1% by mass. <Synthesis of Resin (Α-2) to (Α-11)> In addition to the use of the combination shown in Table 1 and the amount of the monomer (mol%) as a mass, the resin (Α-1) The same method was used to synthesize the resin (Α_2) ~ (A -1 1 ). The Mw, Mw/Mn (molecular weight dispersion), the yield (% by mass) of each of the obtained polymers, and the ratio (mol%) of each of the repeating units in the polymer were measured. These results are shown in Table 2 together with the results of the aforementioned resin (A-1). In the above resins (Α-1) to (A-11), (A-1) to (A-7) correspond to the above-mentioned "resin" and (Α·8) to (A-ll) correspond to the aforementioned "Other resin (A2)". 201013309 s s [Is starting dose (mole%) ΙΓϊ in to in v 投入 input amount (mol%) io 沄沄o JO 1 1 1 1 nmL 2πΐΓ 1- Category 1 — . 1 in s in 1 s To s iT) ή 1 1 1 1 m Input (mol%) Ο O 〇o 1 1 nmL mar Type L . .. v〇ss Buboo s 〇\ i 1 s 1 CN m Input amount (mole %) Ο mooooo ro 〇〇nmL nnrr ! Category 1_ cn inch inch inch inch sm ύ inch i M-10 input amount (mole%) o nmL □ttlf [Category 1 (N ή Τ·Η 1 1 1 S 1 fragrance 1 CN s TH 1 m polymer < (N < m < inch <<;< 卜 < OO. < ON < A-10 < CN m inch in oo 〇 〇 〇rH ^ In m -75- 201013309

Mw/Mn 1.35 1.38 1.39 1.60 1.35 1.40 1.45 1.55 1.45 1.40 Mw 7500 6800 6900 6700 7300 7400 6500 7200 6800 6500 5500 Low molecular weight component (%) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <;0.1<0.1 1 i <0.1 <0.1 <0.1 Content ratio of repeating units derived from each monomer (mol%) Monomer 4 1 43.8 50.7 51.0 39.5 45.9 46.0 1 1 1 1 Monomer 3 45.3 ( Ν On in oo 00 00 18.5 14.2 14.0 1 50.5 51.1 1 Monomer 2 32.9 00 cr: Bu σ\ (N Os OO 〇〇, 49.8 1 35.2 as 06 41.0 Monomer 1 47.2 — 31.0 30.5 32.3 30.7 31.2 50.2 14.3 40.0 59.0 Yield g 66.3 64.5 64.2 65.5 62.0 65.7 65.1 68.4 76.0 65.0 Polymer Al A-2 m < A-4 < A-6 A-7 A-8 A-9 A-10 A-ll —丨― m inch 00 or* i) m e6 -76- 201013309 [1 -2] Modulation of sensitive radiation linear resin composition The resin component (A) is mixed in the ratios shown in Tables 3 and 4 [resin (A 1 ) and (A2) The acid generator (B), the nitrogen-containing compound (D), and the solvent (C) were prepared to prepare the radiation-sensitive linear resin compositions of Examples 1 to 13 and Comparative Examples 1 to 5. [Table 3] Table 3 EXAMPLES Resin component (A) Acid generator (B) 闘 (part)] Nitrogen-containing compound (D) 闘 (part)] Solvent (c) Peripheral (part)] Resin (A1) [Type (part)] Resin (A2) Face (part)] 1 A-2(100) — Bl(4.0) B-2(3.6) D-1(0.70) Cl(1700) C-2(700) C-3(30) 2 A -3(100) — Bl(4.0) B-2(3.6) D-1(0.90) Cl(1700) C-2(700) C-3(30) 3 A-4(100) — B-1( 4.0) B-2(3.6) Dl(0.90) Cl(1700) C-2(700) C-3(30) 4 A-6(100) — B-1(4.0) B-2(3.6) Dl( 0.80) Cl(1700) C-2(700) C-3(30) 5 A-7(100) — B-1(4.0) B-2(3.6) Dl(0.85) Cl(1700) C-2( 700) C-3(30) 6 A-3(100) — B-3(7.5) D-1(0.90) Cl(1700) C-2(700) C-3(30) 7 A-4(100 ) — B-3(7.5) Dl(0.90) C-1(1700) C-2C700) C-3(30) 8 Al(lOO) — B-1(4.0) B-2(3.6) Dl(0.70) Cl(1700) C-2(700) C-3(30) 9 A-2(100) — B-1(4.0) B-2(3.6) Dl(0.65) Cl(1700) C-2(700) C-3(30) -77 - 201013309 [Table 4] Table 4 Resin component (Α) Acid generator (B) Garden (part)] Nitrogen-containing compound (D) [Type (part)] Solvent (c) [ Type (part)] Resin (Α1) 闘(part)] Resin (Α2) Surface (parts) Example 10 Α-5(100) — B-1 (4.0) B-2( 3.6) Dl(0.80) C-1(1700) C-2(700) C-3(30) 11 Α-6(100) — B-1(4.0) B-2(3.6) Dl(0.80) C- 1(1700) C-2(700) C-3(30) 12 Α-2(70) A-9(30) B-1(4.0) B-2(3.6) Dl(0_65) Cl(1700) C -2(700) C-3(30) 13 Α-2(80) A-9(20) B-1(4.0) B-2(3.6) Dl(0.65) Cl(1700) C-2(700) C-3(30) Comparative Example 1 - A-9(100) Bl(4.0) B-2(3.6) D-1(0.70) Cl(1700) C-2(700) C-3(30) 2 — A-10(100) Bl(4.0) B-2(3.6) Dl(0.90) Cl(1700) C-2(700) C-3(30) 3 — A-8(100) B-1 (4.0) B-2(3.6) Dl(0.70) Cl(1700) C-2(700) C-3(30) 4 — A-9(100) B-1(4.0) B-2(3.6) Dl(0.70) Cl(1700) C-2(700) C-3(30) 5 — A-9(90) A-ll(10) Bl(4.0) B-2(3.6) D-1(0.70) Cl(1700) C-2(700) C-3(30)

Further, the details of the acid generator (B), the halogen-containing compound (D) and the solvent (C) shown in Tables 3 and 4 are as follows. In the table, "parts" are quality standards unless otherwise stated. <Acid Generator (B) > (B-1): Triphenylphosphonium • Nonafluoro-n-butanesulfonate-78- 201013309 (Β-2): Triphenylphosphonium 2-(bicyclo[2.2 .1]hept-2'-yl)-1,1-difluoroethanesulfonate (Β-3): triphenylsulfonium 2-(bicyclo[2·2·1]heptan-2'-yl) -1,1,2,2-tetrafluoroethanesulfonate <Solvent (C) > (C-1): Propylene glycol monomethyl ether acetate Lu (C-2): cyclohexanone (C - 3) : γ-butyrolactone <nitrogen-containing compound (D) > (Dl) : Nt-butoxycarbonyl-4-hydroxypiperidine group 7 The substance 1 group was compared with the lipid ratio tree and the sex 13 line 1~. The results of these evaluations are shown in Tables 5 and 6. <Sensitivity> A ruthenium wafer having a film of ARC29 (manufactured by Nissan Chemical Industries, Ltd.) having a thickness of 77 Å was used on the surface of the wafer, and CLEAN TRACK ACT8 (manufactured by Tokyo Electronics Co., Ltd.) was used on the substrate by spin coating. Each of the composition solutions was subjected to PB 'forming a film thickness of 0" 2 μm of a resist film on a hot plate in accordance with the conditions shown in Tables 5 and 6. Next, when the composition solutions of Examples 8 to 13 and Comparative Examples 3 to 5 were used, -79 to 201013309, after the photoresist film was formed as described above, it was washed with pure water for 90 seconds. In addition, when the composition solutions of the examples 1 to 7 and the comparative examples 1 and 2 were used, the upper layer film ("NFC TCX041", manufactured by JSR) was applied to the resist film by a spin coating film to form a film. After baking at a temperature of 90 ° C for 60 seconds, it was washed with pure water for 90 seconds. Then, an ArF excimer laser exposure apparatus "S3 06C" (number of openings: 0.78) manufactured by Nikon was used, and exposure was performed between the mask patterns. After the exposure, the mixture was washed again with pure water for 90 seconds, and PEB was subjected to the conditions shown in Tables 5 and 6, and then washed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23 ° C for 60 seconds. Dry to form a positive photoresist pattern. At this time, in the reticle, the line of the diameter of 0.075 μm and the pitch pattern (1L1S) become the exposure amount of the size of 0.07 5 μm, which is the optimum exposure amount, and the optimum exposure amount is used as the sensitivity. <EL (exposure tolerance)> In the above sensitivity measurement, 线7 5 μιη in the line and pitch pattern, in the range of the optimum exposure amount ± l〇m] / cm 2 , in the range of 1.0 mJ / cm 2 When the number of exposures is changed, the size of the line pattern is plotted with a slope of EL (nm/mJ). <Minimum collapse size (collapse)> In the line and pitch pattern of the above-mentioned sensitivity measurement, when the high exposure amount is irradiated, the CD size of the exposure amount before the ImJ of the exposure amount of the line collapse is generated. The measurement was carried out by 'Measurement Length SEM (manufactured by Hitachi, Ltd., model "S-93 8"). -80- 201013309 The smaller the 値, the better, and it is judged to be good when it is 50 nm or less. <Shape shape of the pattern (pattern shape)> The cross-sectional shape of the line and the pitch pattern of 0.075 μηι in the sensitivity measurement was observed using "S-4 800" manufactured by Hitachi High-Technologies Co., Ltd., and T-top was displayed. When the shape or the dome shape (that is, the shape other than the rectangle) is judged as "defective", when the rectangular shape is displayed, it is judged as "good". <Dissolution amount> As shown in Fig. 1, hexamethyldiazoxide was previously used in a coater/developer (Coat or Developer) (trade name "CLEAN TRACK ACT8", manufactured by Tokyo Electronics Co., Ltd.). The center portion of the 8 吋矽 wafer 1 after the HMDS treatment (100 ° C '60 sec) was placed on the center of the ruthenium rubber sheet 2 having a diameter of 11.3 cm (KUREHA ELASTOMER Co., Ltd. , thickness: 1. 〇mm, shape: unilateral 3 0cm • square). Next, in the hollowed out part of the central part of the rubber sheet 2, use a 10 mL pipette to fill the l〇mL of ultrapure water 3» Figure 11 symbol 11 shows the hexamethyl diazoxide treatment The base diazoxide treatment layer. Then, as shown in FIG. 2, an antireflection film (trade name "ARC29A", manufactured by Bruwer. Science Co., Ltd.) 41 having a film thickness of 77 mm was formed in advance by the above-mentioned coater/developer, and then Example 8 was 13 and the sensitive radiation linear resin compositions of Comparative Examples 3 to 5 were spin-coated on the lower anti-reflection film 41 using the aforementioned coater/developer, and the conditions shown in Tables 5 and 6 were entered into -81 - 201013309 The baking (PEB) treatment is performed to form the tantalum wafer 4 of the photoresist film 42 having a film thickness of 205 nm, and the surface of the photoresist coating film is contacted with the ultrapure water 3, and the ultrapure water 3 is prevented from leaking from the tantalum rubber sheet 2. The state is placed on the enamel rubber sheet 2. This state is maintained for 10 seconds. Then, 8 Å of wafer 4 was taken, and ultrapure water 3 was recovered by a glass syringe, and this ultrapure water 3 was used as an analysis sample. The recovery rate of ultrapure water 3 is 95% or more. Next, a liquid chromatography mass spectrometer (LC-MS, LC part: trade name "SEREIES 1 100" manufactured by AGILENT Co., Ltd., product name "Mariner" manufactured by Perseptive Biosystems, Inc.) was used, and the following measurement was carried out. The peak intensity of the anion portion of the photoacid generator in ultrapure water obtained by the conditions was measured. At this time, the respective peak strengths of the lppb, lOppb, and 100 ppb aqueous solutions of the respective acid generators were measured under the above-described measurement conditions to prepare a calibration curve, and the elution amount of the acid diffusion controlling agent was calculated from the peak intensity using the calibration curve. When the elution amount is 5.0 x 10 12 mol/cm 2 /sec or more, it means "poor", but it does not reach 5. 〇 xl (when T12 mol / cm 2 / sec "is good" (measurement conditions) using a column; trade name "CAPCELL PAK" MG", manufactured by Shiseido Co., Ltd., 1 flow rate; 0.2 ml/min of solvent: 0.1% by mass of formic acid added in water/methanol (volume ratio: 3/7)

Measurement temperature: 35 ° C - 82 - 201013309 <Retraction contact angle > The measurement of the receding contact angle was carried out using a contact angle meter (trade name "DSA-10") manufactured by KRUS Co., Ltd., and was formed in Examples 8 to 13 After the substrate (wafer) of the coating film formed by the respective photosensitive resin compositions of Comparative Examples 3 to 5 was completed, the temperature was rapidly 23 ° C and the humidity was 45%, and the following conditions were normal under normal pressure. The contact angle was measured sequentially. 0 First, the wafer stage position of the contact angle meter is adjusted, and the substrate is set on the adjusted stage. Next, water is injected into the needle, and the position of the needle is finely adjusted to an initial position at which water droplets can be formed on the substrate set as described above. Subsequently, 25 pL of water droplets were formed on the substrate from the needle discharge water, and then the needle was withdrawn from the water droplets, and the needle was retracted to the initial position to be placed in the water droplets. Next, the water droplets were sucked by a needle at a rate of 10 g/miii for 90 seconds while measuring the contact angle of the liquid surface with the substrate once per second (total 90 times). In this way, the average 値 is calculated as the receding contact angle (degree) from the contact angle of φ at the time when the 接触 is stabilized from the contact angle. ° -83- 201013309 Pattern shape Ife Good good & Good good & Mmw 1 1 1 1 1 Grinding 1 cn Dissolution 1 1 1 1 1 1 1 Good good minimum reversal size (nm) Os »rj Os «1 Ό· 〇V£) Bu'Ο \〇msm旦^Ti ^Τί m iTi immersion with the upper membrane for destruction 壊 壊 PEB (temperature / time) 105 ° C / 60 seconds 95 mouth 60 seconds 95 〇 C / 60 seconds - 1 95 ° C / 60 seconds 95. . /60 seconds 95t/60 seconds 95〇C/60 seconds 120°C/60 seconds 105〇C/60 seconds 95〇C/60# 95°C/60 seconds 105〇C/60 seconds 105°C/60 seconds PB (Temperature/Time) 120°C/60 sec 120〇C/60 sec 12 (TC/60 sec 120°C/60 sec 120°C/60 sec 120〇C/60 sec 120t: /60 sec 120°C/ 60 seconds 120. (: / 60 seconds 120 ° C / 60 seconds 120 〇 C / 60 seconds 12 (TC / 60 seconds 120 ° C / 60 seconds (N inch 00 Os 〇m {_习莩❿ο -84- 201013309 9撇

[9S pattern shape is good & bad bad iff iff 诹鹋辎 A 诹鹋辎 w 1 1 00 Dissolution amount 1 1 bad K- good minimum reversal size (nm) ir» m (N Ό ON iTi N j 1 ω I • w^ 卜 · ί / Ί · Sensitivity (mJ) in in 〇〇v〇 immersion with the presence of the upper film m Destroy PEB (temperature / time) 105 ° C / 60 seconds 95 ° C / 60 seconds 12 (TC / 60 seconds 105°C/60 seconds 105°C/60 seconds 1- PB (temperature/time) 120〇C/60 seconds 120°C/60 seconds 120°C/60 seconds 120°C/60 seconds 120°C/ 60 seconds»—Η CN m inch-85- 201013309 It is known from Tables 5 and 6 that the resin composition of the present embodiment containing a resin having a repeating unit (al) having a fluorine atom and an acid dissociable group in a side chain is used. It does not degrade the EL performance, and the pattern collapse performance (minimum collapse size) is excellent. In addition, since it has a repeating unit (al), the water repellency is also excellent, so the liquid immersion exposure is used regardless of the presence or absence of the liquid immersion upper film. [2] Sensitive radiation linear resin composition (II) φ [2-1] Resin synthesis In the following synthesis examples, "(1) Mw and Μη" The measurement of "(2) 13C-NMR analysis" and "(3) The amount of the low molecular weight component derived from the monomer" is carried out in the above-described manner. Each synthesis example will be described below. Resin component (A,) [Resin (A Each of the single systems for the synthesis of -12)~(A-18)] is represented by the following formula (Μ-ll) to (M-18). -86- 201013309

I 2 2 7]

H2C

CH3 HsC

O

O

(M-13)

<Synthesis of Polymer (A-12)>

(M-1 5) 28.82g (l〇mol% (40mol%) is dissolved in 2•丁嗣M_1 1 ) 34_61g (50mol%) of the aforementioned monomer) and the aforementioned monomer (M-14) 36.57g of 2 00g 're-input dimethyl azobisisobutyronitrile 3.38g, s weekly monomer solution. In addition, a 500 mL three-necked flask to which 1 gram of methyl ethyl ketone had been charged was subjected to nitrogen purge for 3 minutes, and after nitrogen rinsing, the reaction vessel was heated to 8 liters under stirring, and the dropping funnel was used for 3 hours. The aforementioned monomer solution prepared beforehand was added. The start of the polymerization was started as the start of the polymerization, and the polymerization reaction was carried out for 6 hours. After the completion of the polymerization, the polymerization solution was cooled by water and cooled to below 3 ° C to be poured into 2 g of methanol. The precipitated white powder was filtered. The white powder after filtration was washed with a slurry of 400 g of methanol twice, filtered, and dried at 5 ° C for 17 hours - 87 - 201013309 to obtain a white powder copolymer (yield 66.3%). The polymer had a Mw of 6800, Mw/Mn=1.32, and 13C-NMR analysis. The content of each repeating unit derived from the monomers (Μ-11), (Μ-15), and (Μ-14) was 47.2. : 7.5 : 4 5.3 (mole %) copolymer. This polymer was used as a resin (Α-12). Further, the content of the low molecular weight component derived from each of the monomers in the resin (Α-12) is less than 0.1% by mass based on 100% by mass of the polymer. <Synthesis of Resin (Α-13)~(Α-18)> In addition to the combination of the combination shown in Table 7 and the amount of input (mol%), the resin (Α-12) The same method was used to synthesize the resin (A-13) ~ ( Α-1 8 ). The Mw, Mw/Mn (molecular weight dispersion), the yield (% by mass) of each of the obtained polymers, and the ratio (mol%) of each of the repeating units in the polymer were measured. These results are shown together with the results of the aforementioned resin (A-1 2 ) as shown in Table 8. In the above resins (Α-12) ~ (A-18), '(Α-12) ~(A-14) and (A-16) are equivalent to the above-mentioned "resin (A1)"' (A-1 5 ) (A-17) and (A-18) correspond to the above-mentioned "other resin (A2)". 201013309

Aw § J Starting dose (% by mole) £ Input (% by mole) 1 1 1 1 〇1 1 nmL nmr Type 1 1 1 1 M-15 1 1 m Input (% by mole) 〇1 o 1 Nml ππίτ Species M-15 M-16 M-17 t M-14 M-14 1 <N si Input (mol%) 〇in iT) CO ntaL πΠΐΓ 1 Type M-14 M-14 M-14 M -14 M-13 M-13 DO 1 ϋ Input (mol%) 〇Ππτί nfflr Type M-11 M-11 M-11 M-11 M-12 M-12 M-12 Polymer A-12 A- 13 A-14 A-15 A-16 A-17 A-18 CN m 2 in Bu OO 镞4□孽-89- 201013309 [oofi Mw/Mn 1.32 1.37 $ 1.35 1.39 1.38 1.31 Mw 6800 7300 7000 7500 6200 6100 1 , 4500 low molecular weight (%) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 W Μ monomer 4 1 coffee 1 1 O) 1 1 t <ήΐι 酹 side N m 酙单体 monomer 3 in 13.9 18.0 1 46.0 51.6 1 monomer 2 45.3 38.6 34.0 52.5 32.0 34.1 1 27.6 monomer 1 47.2 47.5 48.0 47.5 14.1 14.3 72.4 yield g $ cn 〇JO ON «η polymer A-12 A-13 A-14 A-15 A-16 A-17 A-18 m Inch »〇V£) Bu 00 m <n

Q Θ -90- 201013309 [2-2] Preparation of sensitive radiation linear resin composition The resin component (A') [resin (A1) and (A2)], acid generator (B) was mixed in the ratio shown in Table 9. The nitrogen-containing compound (D) and the solvent (C) were prepared to prepare the radiation-sensitive linear resin compositions of Examples 14 to 19 and Comparative Examples 6 to 9. [Table 9]

Table 9 Resin component (A) Acid generator (B) [Type (part)] Nitrogen-containing compound (D) Peripheral (part)] Solvent (c) [Type (part)] Resin (A1) [Type (part) Resin (A2) [Category (Part)] Example 14 A-12(100) — Β-1(9·6) Dl(0.95) Cl(1400) C-2(30) C-3(600) 15 A-13(100) — Bl(9.6) Dl(0.95) Cl(1400) C-2(30) C-3(600) 16 A-14(100) — Β-1(9·6) Dl(0.95 Cl(1400) C-2(30) C-3(600) 17 A-12(50) A-15(50) Β-1(9.6) Dl(0.95) Cl(1400) C-2(30) C-3(600) 18 A-12(70) A-15(30) Β_1(9 and Dl(0.95) Cl(1400) C-2(30) C_3(600) 19 A-16( 100) — Β -2(7.5) D-1(0.65) Cl(1400) C-2(30) C-3_) Comparative Example 6 - A-15(100) Β-1(9.6) Dl(0.95) Cl(1400) C -2(30) C-3(600) 7 A-17(100) Β-2(7.5) D-1(0.65) Cl(1400) C-2(30) C-3(600) 8 — A -15(95) A-18(5) Β-1(9.6) D-1(0.95) Cl(1400) C-2(30) C-3(600) 9 — A-17(95) A-18 (5) Β-2(7_5) Dl(0.65) Cl(1400) C-2(30) C-3(600) -91 - 201013309 In addition, the acid generator (B) and the halogen-containing compound shown in Table 9 The details of (D) and solvent (C) are shown below. In the table, "parts" are quality standards when there is no special description. <acid generator (B) > (B-1): triphenyl mirror • nonafluoro n_butylate ore salt (B-2): triphenylsulfonium 2-(bicyclo[2·2·1] Hept-2'-yl)-1,1-difluoroethanesulfonate_ <Solvent (C) > (C-1) Propylene glycol monomethyl ether acetate (C-2) cyclohexanone (C -3 ) γ-butyrolactone <nitrogen-containing compound (D) > (Dl) Evaluation of Nt-butoxycarbonyl-4-hydroxypiperidinium [2-3]sensitive radiation linear resin composition Example 1 The respective linear radiation resin compositions of 4 to 19 and Comparative Examples 6 to 9 were subjected to various evaluations as follows. The results of these evaluations are shown in Table 10. <Sensitivity> Using a ruthenium wafer having a 7 70 A ARC29 (manufactured by Nissan Chemical Industries, Ltd.) film formed on the surface of the wafer, Examples ～4 to 19 and Comparative Examples 6 to 9-92-201013309 The sensitive radiation linear resin composition was applied onto a substrate by a spin coater using CLEAN TRACK ACT8 (manufactured by Tokyo Electronics Co., Ltd.), and PB was formed on a hot plate under the conditions shown in Table 1 to form a film having a film thickness of 0.1 2 μm. Block the film. It was cleaned by pure water for 90 seconds. Then, an ArF excimer laser exposure apparatus "S306C" (number of openings: 0.78) manufactured by Nikon was used, and exposure was performed in a mask pattern. After exposure, it was washed again with pure water for 90 seconds. After PEB was carried out under the conditions shown in Table 10, it was washed with water and dried by φ from a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23 ° C for 60 seconds. Form a positive photoresist pattern. At this time, in the reticle, the exposure amount of the diameter of 0.075 "1 line and pitch pattern (11^13) becomes a diameter of 0.074111 is the optimum exposure amount, and this optimum exposure amount is used as the sensitivity. <Uniformity of composition (measurement of 1 値)> Examples 14 to 19 and comparison were carried out using a coater/developer (trade name "CLEAN TRACK ACT8", manufactured by Tokyo Electronics Co., Ltd.) Each of the sensitive radiation linear resin compositions of Examples 6 to 9 was spin-coated on a substrate, and baked at 100 ° C for 60 seconds to form two resist films each having a film thickness of about 120 nm (90 to 150 nm). Surface halogen analysis (ESCA) was performed in the depth direction of the film. In the surface element analysis, the amount of secondary electrons generated by X-ray irradiation was measured using a photoelectron spectroscopic device (trade name "Quantum 2000", manufactured by ulvac-phi Co., Ltd.), and the fluorine content F was measured, [the vicinity of the outermost surface ( The fluorine content in the range from the surface side to the film thickness of 3%] and F2 [the outermost surface side of the film thickness of the initial stage to the fluorine content of 20 to 40 nm] (unit: atom%). The measurement angle of -93-201013309 was 90 when measured. . Further, in the F22 measurement, a solvent such as propylene glycol monomethyl ether acetate was applied to the photoresist film after the formation, and the film thickness was measured from the initial film thickness to the predetermined thickness peeling portion. The ratio of the ratio F! to F2 is used as an index indicating the degree of uniformity of the composition, and is defined by K1値 as shown by the following formula (丨).

KpFi/Fz (1) ❹ When this {^値 is satisfied, it means “good” and when it is not satisfied, it means “bad”. <Shape shape of the pattern (pattern shape)> The cross-sectional shape of the line and the pitch pattern of the 0.075 μηι in the sensitivity measurement was observed using the "S-4800" manufactured by Hitachi High-Technologies Co., Ltd. to display the T-top shape. Or a top-rounding shape (that is, a shape other than a rectangle) is judged as "defective", and when a rectangular shape is displayed, it is judged as "good". ® <Dissolution amount> As shown in Fig. 1, hexamethyldioxane (HMDS) treatment was carried out by using a coater/developer (trade name "CLEAN TRACK ACT8", manufactured by Tokyo Electronics Co., Ltd.) in advance. The center portion of the 8 吋矽 wafer 1 after (l〇〇t, 60 sec.) was placed in a circular hollowed out rubber sheet 2 having a diameter of 11.3 cm at the center (KUREHA ELASTOMER, thickness: 1). Omm, shape: 30cm square on one side). Next, in the hollowed out part of the -94-201013309 part of the rubber sheet 2, use 10 mL of a pipette to fill 10 mL of ultrapure water 3. Reference numeral 11 in Fig. 1 denotes a hexamethyldioxane treatment layer after hexamethyldiazepine treatment. Then, as shown in FIG. 2, an antireflection film (trade name "ARC29A", manufactured by Bruwer. Sciences) 41 having a film thickness of 77 mm was formed in advance by the above-mentioned coater/developer, and then Examples 14 to 19 were placed. And the sensitive radiation linear resin composition of Comparative Examples 6 to 9 was spin-coated on the lower anti-φ reflective film 41 using the aforementioned coater/developer, and baked under the conditions shown in Table 10 (PEB). The ruthenium wafer 4 which forms the photoresist film 42 having a film thickness of 205 nm is brought into contact with the ultrapure water 3 on the surface of the photoresist film, and the ultrapure water 3 is prevented from leaking from the ruthenium rubber sheet 2, and is placed in the ruthenium. On the rubber sheet 2. This state is maintained for 1 second. Then, 8 Å of wafer 4 was taken, and ultrapure water 3 was recovered by a glass syringe, and this ultrapure water 3 was used as an analysis sample. The recovery rate of ultrapure water 3 is 95% or more. Next, a liquid chromatography mass spectrometer (LC-MS, LC part: 商品AGILENT company name "SERE IES1100", MS part: Perseptive Biosystems, Inc. The product name "Mariner" manufactured by the product was measured for the peak intensity of the anion portion of the photoacid generator in the obtained ultrapure water under the following measurement conditions. At this time, the respective peak strengths of the lppb, lOppb, and 100 ppb aqueous solutions of the respective acid generators were measured under the above-described measurement conditions to prepare a calibration curve, and the amount of elution was calculated from the peak intensity using the calibration curve. The peak intensity of each of the lppb, lOppb, and lOOppb aqueous solutions of the same nitrogen-containing compound (D-1) was measured under the aforementioned measurement conditions to prepare a calibration curve, and the acid diffusion controlling agent was calculated from the peak intensity using the calibration curve. Dissolution amount -95-201013309 The total amount of these elution amounts is 5.0xl (when T12mol/cm2/sec or more, it is not "poor", and when it is less than 5.0x10-12 mol/cm2/sec, it is not "good" <Measurement conditions > Use column; trade name "CAPCELL PAK MG" (manufactured by Shiseido Co., Ltd.), 1 @ flow rate; 0.2 ml/min of effluent solvent: water/methanol (volume ratio: 3/7) added 〇.1 mass% Formic acid

Measurement temperature: 3 5 ° C <Retraction contact angle> The measurement of the receding contact angle was carried out by using a contact angle meter (trade name "DSA-10") manufactured by KRUS Co., Ltd., and the formation of Examples 14 to 19 and Comparative Example © After the substrate (wafer) of the coating film of the respective linear radiation-sensitive resin compositions of 6 to 9 was quickly measured, the receding contact angle was measured in the following order at room temperature of 23 ° C, humidity of 45%, and normal pressure. First, the wafer stage position of the contact angle meter is adjusted, and the substrate is placed on the adjusted stage. Next, water was injected into the needle, and the position of the needle was finely adjusted to the initial position at which the water droplets could be formed on the set substrate. Then, the water is discharged by the needle, and 25 μί of water droplets are formed on the substrate. Once the needle is pulled out by the water droplets, the needle is lowered to the initial position and placed in the water droplets -96 - 201013309. Next, water droplets were taken by a needle at a rate of 10 pL/min for 90 seconds, and the contact angle between the liquid surface and the substrate was measured once per second (total 90 times). Here, the average 値 of the contact angle of 20 seconds from the point at which the contact angle was measured to be stable was calculated as the receding contact angle (degree). <Number of defects> On the 8 吋矽 wafer on which the lower layer anti-reflection film was formed under the same conditions as the evaluation of the sensitivity described above, each of the radiation-sensitive linear resins of Examples 14 to 19 and Comparative Examples 6 to 9 was used. The film was formed into a film having a film thickness of 1 2 Onm. Next, the film was washed with pure water for 90 seconds. Then, this film was subjected to an ArF excimer laser immersion exposure apparatus ("NSR S3 06C", manufactured by NIKON Co., Ltd.) with a mask pattern of ΝΑ = 0·75, σ = 〇·85, 1/2 Annular. Exposure. After the exposure, the mixture was washed with pure water for 90 seconds, and PEB was carried out under the same conditions as the evaluation of the sensitivity described above. Then, it was developed by a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23 ° C for 30 seconds, washed with water, and dried to form a positive resist pattern. At this time, the exposure amount of the hole pattern having a width of 1 〇〇〇 nm is the optimum exposure amount. With this optimum exposure amount, a hole pattern of a width of 1 〇〇 Onm is formed on the wafer as a defect inspection wafer. In addition, this length measurement system uses a scanning electron microscope ("S-9380", manufactured by Hitachi High-Technologies Corporation). Then, "KLA2351" manufactured by KLA-Tencor Co., Ltd. was used to measure the number of defects on the wafer for defect inspection. Further, a scanning electron microscope ("S-93 80", manufactured by Hitachi High-Technologies Co., Ltd.) was used to observe that the defects measured by "KLA235 1" were classified as being determined to be from a photoresist and foreign matter from the outside. After the classification, it is judged as "poor" when the total number of the photoresistors (the number of defects) is -97-201013309 100/wafer or more, and it is judged as "good" when it is less than one/wafer. . Further, the defect from the photoresist refers to a residue-like defect from the dissolution residue at the time of development, a protrusion-like defect from the dissolution residue of the resin in the photoresist solvent, and the like, and the defect from the outside means the garbage from the dust in the atmosphere and Coating spots, bubbles, etc., defects in a form unrelated to photoresist. -98- 201013309

s 1 number of defects L 1 里1 ι&&&&&&&& 13⁄4 • π^ -03⁄4 π^ κ- ¢: Huan A 琅 marriage to CO 〇 〇 § Γ Γ I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I ^ & -23⁄4 n^ Stele K- }f to Helmet &&&&& Wake up • π^ D^ -13⁄4 • n^ {13⁄4 K- 茂之均一程 (K, ifi) ^JN rH ί? CN /—·Ν oi 0? <N ίτΓ ON ss δ & £ S £ s -13⁄4 ¢03⁄4 {¢( n^ ·〇£( }f K- m S (N m cn m 〇ο 〇 § 〇ο 急ο Ο 念 gt ν〇VO νο v〇S乸PP Ρ Ρ Ρ P Ρ .. PP g rH 宕rH to 1-H 1—4 ^-H 1—Η Shovel Ο 〇®卺 〇卺 〇卺 Q Q Q Q 〇 〇 Ρ Ρ Ρ Ρ Ί Η Η Ρ Ρ β 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 〇 〇〇 〇〇 Os 'Ο 〇〇〇 〇〇〇 舾 μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ μ A photoresist film having a small h-thin and a high uniformity in the film thickness direction can be obtained. The photoresist film obtained by using such a composition does not deteriorate the dissolution inhibition ability and is excellent in the control of the number of defects. In addition, the photoresist film is also excellent in water repellency, and has a high receding contact angle. Therefore, it can be expected to have good performance in the case of immersion exposure with or without the use of the liquid immersion film. [Simple description of the drawing] Fig. 1 is a view showing a state in which the elution amount of the coating film formed by the sensitive radiation linear resin composition of the present invention is measured, and the ultrapure water is prevented from leaking, and the state of the wafer is placed on the polysiloxane rubber sheet. [Fig. 2] is a cross-sectional view showing a state in which the amount of elution of the coating film formed by the sensitive radiation linear resin composition of the present invention is measured. [Description of main component symbols] 1: 矽 wafer, 11: hexa A quinone amide treatment layer, 2: a polyoxyethylene rubber sheet, 3: ultrapure water, 4: germanium wafer, 41: antireflection film, 42: photoresist film. -100-

Claims (1)

201013309 VII. Patent application scope: 1 · ~ A liquid immersion exposure linear radiation resin composition containing (A) resin component, (B) sensitive radiation linear acid generator, (C) solvent sensitive radiation linear resin In the composition, the resin component (A) is an acid-containing compound having a repeating unit (al) having a fluorine atom and an acid dissociable group in a side chain, when the total amount of the resin component (a) is 1% by mass. The dissociable group-containing resin (A1) contains more than 50% by mass. The sensitive radiation linear resin composition for liquid immersion exposure according to the first aspect of the invention, wherein the acid-dissociable group-containing resin (A1) contains a repeating unit represented by the following general formula (1) as the above repeating unit (al), [chemical 1] [In the general formula (1), η represents an integer of 1 to 3, R1 represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and R2 represents a single bond or a carbon number of 1 to 10 (η+1). a straight-chain, branched or cyclic saturated or unsaturated hydrocarbon group, R3 represents a single bond, or a linear, branched or cyclic saturated or unsubstituted carbon number of 1 to 2 a saturated hydrocarbon group, X represents a methyl group substituted by a fluorine atom, or a linear or branched fluorine alkyl group having a carbon number of 2 to 20, and a γ system represents a single-101 - 201013309 M, and the present -η is At 1 o'clock, R4 represents an acid dissociable group, and when η is 2 or 3, r4 is a hydrogen atom or an acid dissociable group independently of each other, and at least one R4 acid dissociable group is present. 3. The sensible radiation linear resin composition for liquid immersion exposure of the second aspect of the invention, wherein the acid-dissociable group-containing resin (Α1) contains a repeating unit represented by the following general formula (1-1) as the foregoing a repeating unit represented by the general formula (1), [Chemical 2] [In the general formula (1-1), η represents an integer of 1 to 3, R1 represents a hydrogen atom, a methyl group or a trifluoromethyl group, and R3 represents a single bond or a carbon number of 1 to 20; a linear, branched or cyclic saturated or unsaturated hydrocarbon group, X represents a methyl group substituted by a fluorine atom, or a linear or branched fluorine alkyl group having a carbon number of 2 to 20, η When it is 1, R4 represents an acid dissociable group, and when η is 2 or 3, R4 represents a hydrogen atom or an acid dissociable group independently, and at least one R4 is an acid dissociable group, and R5 represents a carbon number of 3~. a linear, branched or cyclic saturated or unsaturated hydrocarbon group of (η+1) valence of 10]. 4. The sensitive radiation linear resin composition for immersion exposure according to the second or third aspect of the invention, wherein the acid-dissociable group-containing resin (Α1) contains a repeating unit represented by the following general formula (1-2) as The above-mentioned general formula (1) Table-102-201013309 shows the repeating unit, [Chemical 3 1 (1-2) In the general formula (1-2), R1 represents a hydrogen atom, a methyl group or a group, and R6 represents a single bond or a linear or bicyclic ring having a carbon number of 1 to 20 The saturated or unsaturated hydrocarbon group, X represents a linear or branched fluoroalkyl group having a methyl group or a carbon number of 2 to 20, and an acid dissociable group. 5. The liquid immersion radiation linear resin composition according to any one of claims 2 to 4, wherein the acid-dissociable group-containing tree contains a repeating unit represented by the following general formula (1-3) as The repeating unit represented by the above formula (1), (1-3) [In the general formula (1-3), R1 represents a hydrogen atom, a methyl group, or a trifluoromethyl branch-chain extension. Lipid (A1 is generally referred to as [Chemical 4] Trifluoromethyl-103-201013309, R6 represents a single bond, or a linear, branched or cyclic saturated or unsaturated hydrocarbon group having a carbon number of 1 to 20, and X is substituted by a fluorine atom. A methyl group or a linear or branched fluoroalkyl group having 2 to 20 carbon atoms, and R 7 is an acid dissociable group. 6. A method for forming a photoresist pattern, characterized in that: (1) forming a light on a substrate by using a linear radiation resin composition for liquid immersion exposure according to any one of claims 1 to 5; The step of blocking the film, (2) the step of subjecting the photoresist film to immersion exposure, and (3) the step of developing the photoresist film after immersion exposure to form a photoresist pattern. 7. A polymer characterized by comprising a repeating unit represented by the following general formula (1) and a repeating unit having a lactone skeleton, [Chemical 5] / R1, [In the general formula (1), η represents an integer of 1 to 3, R1 represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and R2 represents a single bond or a carbon number of 10 (η+ 1) a linear, branched or cyclic saturated or unsaturated hydrocarbon group of a valence, and R3 represents a single bond, or a linear, branched or cyclic saturated or divalent carbon number of 1 to 20 An unsaturated hydrocarbon group, X represents a methyl group substituted by a fluorine atom, or a linear or branched fluorine alkyl group having a carbon number of 2 to 20, and the lanthanide series is a single 104-201013309 bond, or -CO - When η is 1, R4 means that the acid dissociable group 'η is 2 or 3, and R4 independently represents a hydrogen atom or an acid dissociable group ' and at least one quaternary 4 is an acid dissociable group. 8. A sensitive radiation linear resin composition characterized by a photosensitive radiation linear resin composition used for forming the photoresist film in a method for forming a photoresist pattern of the following step, the photoresist pattern The forming method comprises a liquid immersion exposure step of irradiating the photoresist film formed on the substrate with a radiation having a refractive index higher than that of the liquid immersion exposure liquid at a wavelength of 193 nm. The sensitive radiation linear resin composition contains (A') a resin component, (B) a radiation sensitive linear acid generator, and (C) a solvent, and the (A') resin component contains a fluorine atom and an acid dissociation in a side chain. The acid-dispersing group-containing resin (A1) of the repeating unit (al), and the above-mentioned radiation-sensitive linear resin composition is satisfied by the definition of the following formula (i), K1 = F 1 / F2 (i) [In the formula (i), F! represents the fluorine content (ato%) near the outermost surface of the photoresist film produced by the following surface element analysis and calculation of the following conditions: 'F2 The system is determined by the following surface element analysis The calculated fluorine content (ato%) from the outermost surface side of the photoresist film to about 20% of the film thickness] -105 - 201013309 (condition for producing a photoresist film): spin-coating the sensitive radiation linear resin composition The substrate was baked at 100 ° C for 60 seconds to prepare a photoresist film having a thickness of about 120 nm. (Surface element analysis): X-rays were irradiated to the photoresist film using a photoelectron spectroscope, and the amount of secondary electrons generated was measured. The amount of fluorine atoms in the photoresist film was measured. 9. A photoresist film comprising a liquid immersion exposure liquid having a refractive index higher than that of air at a wavelength of 193 nm, and a liquid immersion exposure step of irradiating a light ray film formed on the substrate to expose the radiation The above-mentioned photoresist film used in the method for forming a photoresist pattern is characterized in that K2 of the following formula (Π) is one satisfying 1$K2S5, K2 = F3/F4 (ii) [Formula (ii) In the case of F3, the fluorine content (atom%) in the vicinity of the outermost surface of the photoresist film measured and calculated by the following surface element analysis is shown, and F4 is shown and analyzed by the following surface element analysis. From the outermost surface side of the photoresist film to the atomic percentage near 20% of the film thickness (surface element analysis): X-ray is irradiated to the photoresist film using a photoelectron spectroscope, and the generated secondary electrons are measured. The amount of fluorine atoms in the photoresist film was measured. -106-