TW201219972A - Resist pattern formation method and radiation-sensitive resin composition - Google Patents

Abstract

The present invention provides a resist pattern formation method comprising: (1) a resist film formation step of applying a radiation-sensitive resin composition to a substrate; (2) an exposure step; and (3) a step of developing using a developing solution containing 80 mass% or more of an organic solvent; wherein the radiation-sensitive resin composition includes: [A] a base polymer having an acid-dissociable group; [B] a radiation-sensitive acid generator containing a cation and an anion, the anion having an alicyclic group and the ratio (F/C) of fluorine atoms and carbon atoms of the anion being 0.1 to 0.5; and [C] a fluorine-containing polymer in which the content ratio of fluorine atoms is higher than that of the polymer of [A].

Description

201219972 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a photoresist pattern forming method and a radiation sensitive resin composition. [Prior Art] With the miniaturization of various electronic devices such as semiconductor devices and liquid crystal devices, the miniaturization of the photoresist pattern in the lithography step is required. At present, for example, an ArF excimer laser can be used to form a fine photoresist pattern having a line width of about 90 nm, but in the future, a finer photoresist pattern is required. On the other hand, according to the immersion exposure, even if a light source of the same exposure wavelength is used, the same high resolution as when a light source of a shorter wavelength is used can be achieved. For this reason, liquid immersion exposure has been attracting attention as a technique for reducing cost and achieving high resolution in the manufacture of semiconductor components requiring expensive equipment investment. However, it is considered that liquid immersion exposure is due to the liquid contained in the photoresist. The dissolution of the immersion medium causes the photoresist film to deteriorate and its performance is degraded. The dissolved material changes the refractive index of the liquid immersion medium locally, and the dissolved material contaminates the surface of the photoresist, thereby adversely affecting the characteristics of the lithography. Defects (refer to International Publication No. 04/0 6 8 242). For the solution strategy of this defect, it is considered to improve the resolution by utilizing the characteristics of the chemically amplified photoresist material. As for this technique, for example, a double exposure technique and a dual patterning technique are known. Among them, the technique of improving the resolution without increasing the number of steps of using the existing device reveals the technique of using an organic solvent having a polarity lower than that of the alkaline aqueous solution in the developing solution-5-201219972 (refer to Japanese Laid-Open Patent Publication No. 2000-199953) . This can improve the optical contrast by using an organic solvent, and the result becomes a person who can form a fine pattern. However, when such an organic solvent is used to form a photoresist pattern, when a conventional resin composition is used in a photoresist film, a hole pattern which causes an unresolved image is formed, and a so-called missing contact hole occurs. Defects In the above-described developing solution, an organic solvent is used to form a photoresist pattern, and a combination of a method for forming a photoresist pattern capable of suppressing occurrence of a wrong contact hole and a composition for a radiation sensitive resin has not been found so far. [PRIOR ART DOCUMENT] [Patent Document 1] International Publication No. 04/068242 [Patent Document 2] JP-A-2000-99953 [Summary of the Invention] [Problems to be Solved by the Invention] The present invention is Based on the above problems, the object of the invention is to provide a method for forming a photoresist pattern which can reduce the occurrence of a wrong contact hole and which has excellent lithographic characteristics when using a developing solution containing an organic solvent, and a radiation sensitive resin composition. Things. [Means for Solving the Problem] The invention for solving the above problems is: A method for forming a photoresist pattern, which comprises the following steps: a photoresist pattern -6-201219972 type forming method: (1) coating a radiation sensitive/inductive property on a substrate a photoresist film forming step of the resin composition, (2) an exposing step, and (3) a step of developing using a developing liquid containing 80% by mass or more of an organic solvent, and characterized by the above-mentioned radiation-sensitive resin composition The substance contains: [A] a base polymer having an acid-dissociable group (hereinafter sometimes referred to as "[A] polymer"), [B] an anion having a cation and an alicyclic group, and a fluorine atom of the anion A radiation-sensitive acid generator having a ratio of atoms to carbon atoms (F/C) of 0.1 or more and 0.5 or less (hereinafter sometimes referred to as "[B] acid generator"), and [C] containing fluorine atoms and fluorine A polymer having a higher atomic content than the [A] polymer (hereinafter sometimes referred to as "[C] polymer"). The [B] acid generator contained in the radiation sensitive resin composition has an alicyclic group and an anion having a fluorine atom to carbon atom atomic ratio (F/C) of 0.1 or more and 0.5 or less. By causing the [B] acid generator to contain the above specific structure, the acid generated from the [B] acid generator at the time of exposure dissociates the acid-dissociable group of the [A] polymer, and the formation of the organic solvent-containing compound can be formed. Like a liquid, it becomes a poorly soluble photoresist pattern. The reason why the occurrence of the wrong contact hole is suppressed by the above-mentioned specific structure of the [B] acid generator is not clear, but it is considered that the hydrophobicity of the [B] acid generator having the F/C within the above specific range becomes moderate. The range is such that the [B] acid generator is prevented from being localized on the surface of the photoresist film 201219972' and the compatibility with the [A] polymer is improved by making the [B] acid generator have a ring-shaped group. The [B] acid generator is uniformly dispersed in the photoresist film. As a result, the occurrence of the wrong contact hole can be effectively prevented by suppressing the deprotection reaction of the specific polymer on the outermost surface of the photoresist film. Further, by using a [C] polymer having a fluorine atom content higher than that of the [A] polymer, the [C] polymer is localized on the surface of the photoresist film when the photoresist is applied, and the photoresist can be rendered water-repellent. A photoresist film suitable for exposure by immersion can be formed. According to this, in the method for forming a resist pattern which is developed using a developing liquid containing 80% by mass or more of an organic solvent, by combining the above-described composition having a specific structure, occurrence of a wrong contact hole can be suppressed and microfabrication can be formed. A photoresist pattern with excellent shadow characteristics. [A] The acid dissociable group of the polymer preferably has a monocyclic or polycyclic alicyclic hydrocarbon group. According to this, excellent acid dissociation property and sufficient sensitivity can be obtained. [B] The anion of the acid generator is preferably represented by the following formula (1). 【化1】

R1--C-j-S03' (1)

(In the formula (1), R1 is a monovalent organic group having a monocyclic or polycyclic alicyclic group, and η is 1 or 2'. Rfl& Rf2 are each independently a hydrogen atom, a fluorine atom or a carbon number of 1 to 4. When the fluorinated alkyl group is a hydrogen atom, when 1^1 and 1^2 are each a hydrogen atom, when both 1^1 and Rf2 are plural, the plural Rfl& Rn may be the same or different) 使 by [B The anion of the acid generator has the specific structure described above, and the -8 - 201219972 [B] acid generator is more uniformly dispersed in the photoresist film, and the localization of the acid in the exposed portion can be effectively suppressed. The anion having an alicyclic group of the acid generator is preferably at least one anion selected from the group consisting of anions represented by the following formulas (2) to (5). [Chemical 2]

(4)

【化5】

0

F2C, S03- (5) [B] acid generator can further improve the dispersibility of [B] acid generator in the photoresist film by containing the above specific anion' and further improve the error of the contact hole - 201219972 Inhibition. The organic solvent contained in the above-mentioned developing solution is preferably at least one selected from the group consisting of an alcohol solvent, an ether solvent, a ketone solvent, a guanamine solvent, an ester solvent, and a hydrocarbon solvent. By using such a specific organic solvent, an appropriate combination with a specific photoresist composition can be achieved, and a more excellent photoresist pattern of lithography can be obtained. Further, the radiation sensitive resin composition of the present invention is characterized by comprising the following component = [A] a base polymer having an acid dissociable group, [B] an anion having a cation and an alicyclic group, and the anion a radiation-sensitive acid generator having a fluorine atom to carbon atom atomic ratio (F/C) of 0.1 or more and 0.5 or less, and [C] a polymer having a fluorine atom and having a fluorine atom content higher than that of the [A] polymer . According to the radiation sensitive resin composition, in the method of forming a photoresist pattern using a developing solution containing an organic solvent, occurrence of a wrong contact hole can be effectively suppressed. [Effect of the Invention] The present invention is suitable for use as a liquid immersion exposure, and can be provided in a method of forming a photoresist pattern having less occurrence of erroneous contact holes and excellent lithography characteristics when using a developing solution containing an organic solvent, and radiation sensitivity. Resin composition. [Embodiment] -10-201219972 <Formation Method of Photoresist Pattern> The present invention is a step of forming a photoresist film comprising (1) coating a radiation-sensitive resin composition on a substrate, (2) an exposure step, and ( 3) a photoresist pattern forming method using a developing solution containing an organic solvent of 80% by mass or more, and characterized in that the radiation sensitive resin composition contains [A] having an acid dissociable group. a base polymer, [B] a radiation-sensitive acid generator containing a cation and an anion having an alicyclic group, and having an atomic ratio (F/C) of a fluorine atom to a carbon atom of the anion of 0.1 or more and 0.5 or less, And [C] a polymer containing a fluorine atom and having a fluorine atom content higher than that of the [A] polymer. Each step is detailed below. [Step (1)] In this step, the composition used in the present invention is applied onto a substrate to form a photoresist underlayer film. As the substrate, a conventionally known substrate such as a tantalum wafer or a crystal covered with aluminum can be used. Further, an organic or inorganic antireflection film is formed on the substrate as disclosed in Japanese Patent Publication No. Hei 6-12452 or JP-A-59-93448. The coating method is exemplified by spin coating (S p i n c 〇 a t i n g), casting coating, roll coating, and the like. Further, the film thickness of the formed photoresist film is usually 0.01 μm to Ιμιη, preferably 0_01μηι to 0·5 μιη. After coating the composition, the solvent in the coating film may be volatilized by pre-baking (ΡΒ) as needed. The heating condition of the crucible is suitably selected depending on the composition of the composition, but it is usually from 30 ° C to 200 ° C, preferably from 50 ° C to 150 ° C. In order to prevent the influence of the alkaline impurities and the like contained in the environmental atmosphere, a protective film disclosed in, for example, Japanese Laid-Open Patent Publication No. Hei-5-8 8 8 98 can be provided on the photoresist layer of -11 - 201219972. For the prevention of the outflow of the acid generator or the like from the photoresist layer, a protective film for liquid immersion disclosed in, for example, JP-A-2005-3 5 23 84 can be provided on the photoresist layer. Again, these techniques can be employed. [Step (2)] This step is to expose the desired area of the photoresist film formed in the step (1) through a mask of a specific pattern and a desired liquid immersion liquid by shrinking the projection. For example, the hole pattern is applied to the substrate on which the photoresist is applied, and is subjected to reduced projection exposure through a desired dot pattern mask, and is obtained by development. Further, the groove pattern can be formed by reducing the projection exposure through a contour mask, for example, in a desired region, thereby forming an equal groove pattern. Exposure can also be performed more than twice with the desired pattern and mask pattern. When two or more exposures are performed, it is preferred to continuously perform exposure. In a plurality of exposures, for example, the first reduction projection exposure is performed through the line and the interval pattern mask on the desired area, and then the exposure portion for performing the first exposure is performed for the second time in such a manner that the lines intersect. In order to reduce the projection exposure, in particular, the first exposure portion and the second exposure portion are preferably orthogonal to each other, and a circular contact hole pattern can be formed in the unexposed portion surrounded by the exposure portion. Further, the liquid immersion liquid used for the exposure is exemplified by water or a fluorine-based inert liquid. The liquid immersion liquid is transparent to the exposure wavelength, and in order to keep the deformation of the optical image projected on the film to a minimum, it is preferable that the temperature coefficient of the refractive index is as small as possible, but especially the exposure light source is ArF excimer. In the case of laser light (wavelength 193 nm), in addition to the above viewpoints, it is easy to obtain and easy to operate, and it is preferable to use -12-201219972 for water. The water used is preferably distilled water. The radiation used in the exposure is appropriately selected depending on the type of the [B] acid generator, and is exemplified by ultraviolet rays, far ultraviolet rays, X rays, charged particle beams, and the like. The above is preferably a far ultraviolet ray represented by an ArF excimer laser or a KrF excimer laser (wavelength 248 nm), more preferably an ArF excimer laser. The exposure conditions such as the amount of exposure are appropriately selected depending on the composition of the composition, the type of the additive, and the like. In the pattern forming method of the present invention, there may be a plurality of exposure steps, the same light source may be used for the plurality of exposures, and different light sources may be used, but the first exposure preferably uses ArF excimer laser light. Further, it is preferred to perform post-exposure baking (PEB) after exposure. By carrying out PEB, the dissociation reaction of the acid dissociable group in the composition proceeds smoothly. The heating condition of PEB is usually 3 (TC to 200 ° C, preferably 50 ° C to 170 ° C. [Step (3)] This step is used after the exposure of the step (2) contains 80 mass ° /. The negative-type developing solution of the above organic solvent is developed to form a resist pattern. The negative-type developing solution is a solution for selectively dissolving and removing the low-exposure portion and the unexposed portion. The organic solvent to be used in the liquid is preferably at least one selected from the group consisting of an alcohol-based agent, an ether-based solvent, a ketone-based organic solvent, a guanamine-based solution, an ester-based organic solvent, and a hydrocarbon-based solvent. For example: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, tert-butanol, n-pentanol, isoamyl alcohol, 2-methylbutanol, second -13- 201219972 pentanol, third pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, second hexanol, 2-ethylbutanol, second heptanol, 3-g Alcohol, n-octanol, 2-ethylhexanol, second octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-nonanol, second-undecyl alcohol, trimethyl Sterol, second-dodecanol, a mono-alcohol solvent such as a second-heptadecanol, decyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol or diacetone alcohol; Glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4- a polyvalent alcohol solvent such as heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol or triethylene glycol 'tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, two Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol An oxime ether solvent such as monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether or the like, and a polyvalent alcohol partial ether solvent Listed as, for example, diethyl ether, dipropyl ether, dibutyl ether 'diphenyl ether, etc.. The solvent is exemplified by, for example, acetone, 2-butanone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, ethyl n-butyl ketone. , methyl n-hexyl ketone, diisobutyl ketone, trimethyl fluorenone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4- -14- 201219972 A ketone solvent such as diketone, etidylacetone or acetophenone. The guanamine solvent is exemplified by, for example, N,N'-dimethylimidazolidinone, N-methylformamide, N,N-dimethyl Formamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methyl Pyrrolidone and the like are ester solvents such as diethyl carbonate, propyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, acetic acid. Butyl ester, isopropyl acetate 'amyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, second amyl acetate, 3 - methoxybutyl acetate, methyl amyl acetate, acetic acid 2 -ethyl butyl ester, 2-ethylhexyl acetate, B Benzyl acrylate, cyclohexyl acetate, methylcyclohexyl acetate, n-decyl acetate, methyl acetoxyacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol single Ethyl ether ester, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate 'propylene glycol single Ethyl ether ester, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid glycol ester, acetic acid methoxy three - glycol ester, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate , diethyl malonate, dimethyl phthalate, diethyl phthalate, and the like. The hydrocarbon solvent is exemplified by, for example, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, and ring. Hexane, methylcyclo-15-201219972 An aliphatic hydrocarbon solvent such as hexane; benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, An aromatic hydrocarbon solvent such as isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene or n-pentylnaphthalene, etc., such as methyl amyl ketone and acetic acid Butyl ester, isopropyl acetate, and amyl acetate are preferred. These organic solvents may be used singly or in combination of two or more kinds. The content of the organic solvent in the developing solution is preferably 80% by mass or more, more preferably 85% by mass or more, and still more preferably 90% by mass or more. When the organic solvent contained in the developing solution falls within the above range, the unexposed portion can be effectively dissolved and removed, and a photoresist pattern excellent in development characteristics and lithography characteristics can be formed. Further, as a component other than the organic solvent, for example, an appropriate amount of a surfactant may be added to the photographic solution such as water or eucalyptus oil. The surfactant is exemplified by an ionic or nonionic fluorine-based surfactant and/or a lanthanoid surfactant. The development method is exemplified by a method in which a substrate is immersed in a bath filled with a developing liquid for a certain period of time (immersion method), and a method in which a developing liquid is filled on a surface of a substrate by a surface tension and is stationary for a predetermined period of time (a paddle stirring method). A method of spraying a developing solution onto a surface of a substrate (spraying method), rotating at a constant speed, and scanning a developing solution at a constant speed to apply a developing solution to a substrate (dynamic coating method) )Wait. In the photoresist pattern forming method, it is preferable to wash the photoresist film with a washing liquid after the development of the step (3) -16-201219972. Further, the washing liquid in the washing step may be an organic solvent, and the generated dross may be effectively washed. The washing liquid is preferably a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent or a guanamine solvent. Among these, an alcohol solvent and an ester solvent are preferable, and a monovalent alcohol solvent having a carbon number of 6 to 8 is more preferable. The one-valent alcohol having 6 to 8 carbon atoms is exemplified by a linear, branched or cyclic one-valent alcohol, and is exemplified by, for example, 1-hexanol, 1-heptanol, 1-octanol, 4-methyl-2. Pentanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, benzyl alcohol, and the like. Among these, p-hexyl alcohol, 2-hexanol, 2-heptanol, and 4-methyl-2-pentanol are preferred. The components of the above washing liquid may be used singly or in combination of two or more. The water content in the washing liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 3% by mass or less. By setting the water content to 1% by mass or less, good development characteristics can be obtained. Further, an interfacial surfactant to be described later may be added to the washing liquid. The method of the cleaning treatment is, for example, a method of applying a washing liquid to a substrate rotating at a constant speed (a spin coating method), a method of immersing the substrate in a tank filled with a washing liquid for a certain period of time (dipping method), and a substrate. A method of spraying a washing liquid on a surface (spraying method) or the like. <Ray-sensitive resin composition> The radiation-sensitive resin composition used in the present invention contains [A] a polymer, a [B] acid generator, and a [C] polymer. The [A] polymer has an acid dissociable group, and the acid dissociable group is dissociated by the action of an acid generated from the [B] acid generator to increase the polarity of the [A] polymer. [B] The acid generator contains a cation and an anion having an alicyclic group from -17 to 201219972, and the atomic ratio (F/C) of the fluorine atom to the carbon atom of the anion is 0 · 1 or more 〇 5 or less It does not localize to the surface of the photoresist film but is uniformly dispersed, and has good compatibility with the [A] polymer due to having an alicyclic group. [C] The polymer contains a fluorine atom, and the fluorine atom content ratio is higher than that of [A] polymer, so it can be localized on the surface of the photoresist film to impart water repellency and contribute to proper photoresist by immersion exposure. The formation of a film. Further, the composition may contain any component as long as it does not impair the effects of the present invention. Each component is detailed below. <[A] Polymer> [A] The polymer is a structural unit containing an acid-dissociable group, and the acid dissociable group is dissociated by an action of an acid to increase the polarity of the base polymer. Further, the term "base polymer" means a polymer which constitutes a main component in a polymer of a resist pattern formed of a radiation sensitive resin composition. It is preferable to mean that the polymer accounts for 50% by mass or more of the total of the polymers constituting the photoresist pattern. In addition, the "acid dissociable group" is a group which substitutes a hydrogen atom in a polar functional group such as a carboxyl group, and means a group which is dissociated by the action of an acid generated from the [B] acid generator by exposure. The specific acid-dissociable group which the [A] polymer has is exemplified by a group represented by the following formula (7). [Structural unit (I)] [A] The structural unit having an acid dissociable group of the polymer is exemplified by a structural unit (I) represented by the following formula (6). -18- 201219972 【化6】

(In the formula (6), R2 is a hydrogen atom, a methyl group or a trifluoromethyl group RP is an acid dissociable group). The acid dissociable group represented by the above RP is preferably a group represented by the following formula (7). (7) RP1—C—RP3 RP2 (In the formula (7), RP1, Rp2 and RP3 are alkyl groups having 1 to 4 carbon atoms, and carbon atoms of 4 to 20 are one-valent alicyclic hydrocarbon groups or carbon numbers. 4 to 20 one-valent heterocyclic group, RP2 and RP3 may be bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms together with the carbon atoms bonded thereto. The alkyl group having 1 to 4 carbon atoms represented by RP1, RP2 and RP3 is exemplified by, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropane. Base, third butyl, etc. The above-mentioned ones having a carbon number of 4 to 20 represented by RP1, RP2 and RP3 are exemplified by a polycyclic ring having a bridging skeleton such as an adamantane skeleton or a norbornane skeleton. -19-201219972 alicyclic group: A monocyclic alicyclic group having a cycloalkane skeleton such as cyclopentane or cyclohexane. Further, these groups may be substituted with, for example, one or more of linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms. The one-valent heterocyclic group having 4 to 20 carbon atoms represented by RP1, RP2 and RP3 is exemplified by a group represented by the following formula. In the following formula, η represents an integer of 〇~3, and X represents an oxygen atom or a methylene group. 【化8】

X

As for the above formula (7), RP1 is preferably an alkyl group having 1 to 4 carbon atoms, and RP2 and RP3 are bonded to each other to form a divalent group having an adamantane skeleton or a cycloalkane skeleton together with each of the bonded carbon atoms. The structural unit (I) is exemplified by a structural unit represented by the following formula (6 -1 ) to (6 - 4 ) -20- 201219972

(In the formulae (6-1) to (6-4), R2 is synonymous with the above formula (6), and RP1, RP2 and RP3 are synonymous with the above formula (7), and np is an integer of 1 to 4). The structural unit represented by the above formula (6) or (6-1) to (6-4) is, for example, a structural unit represented by the following formula. -21 - 201219972 【化1 0】

R2 R2 R2 R2

R2 R2 R2

-22- 201219972 【化1 1】 R2 R2 R2

R2 R2

O R2

[A] In the polymer, the content of the structural unit (I) is preferably more than 10 mol% relative to the total structural unit 'I structural unit (I) constituting the polymer of -23-201219972. Ear %~60% of the ear. Further, the [A] polymer may have one type or two or more types of structural units (I). [Structural unit (II)] [A] The polymer preferably has a structural unit (II) having a lactone structure and/or a cyclic carbonate structure. By having such a structural unit (II), the adhesion of the photoresist film to the substrate can be improved. Here, the lactone structure means a cyclic group containing one ring (lactone ring) having a -O-C(O)-structure. The lactone is counted as one ring, and is referred to as a monocyclic group when it is only a lactone ring, and is also called a polycyclic group irrespective of its structure when it has other ring structures. The structural unit (II) having a lactone structure is exemplified by a structural unit represented by the following formula. -24- 201219972 【化1 2】 RL1 RL1 rL1

Rl1

O

rL1 RL1 rL1 rL1

o o 〇 (wherein RU is a hydrogen atom, a methyl group or a trifluoromethyl group). -25- 201219972 The monomer which produces the structural unit (Π) containing a lactone structure is exemplified by the compound represented by the following formula (L-1).

(In the formula (L-1), RL1 is a hydrogen atom, a methyl group or a trifluoromethyl group 'RL2 is a single bond or a divalent linking group, and RL3 is a monovalent organic group having a lactone structure) = two represented by RL2 The valence linking group is, for example, a divalent linear or branched hydrocarbon group having 1 to 20 carbon atoms. The one having a lactone structure represented by rL3 is exemplified by the following formula (L3-1) to (L3). -6) The basis of the representation. •26- 201219972 【化1 4】 Take

*

(L3-2) ♦

(In the formula (L3-1) to (L3-6), RLcl is an oxygen atom or a methylene group 'RLc2 is a hydrogen atom or an alkyl group of carbon number, nLci is 〇 or 1, and nLe2 is an integer of 〇~3 '* indicates that the above formula (L_1) is bonded to the bonding position of RL2, and 'the group represented by the formula (L3-1) to (L3-6) may have a substituent). The monomer of the structural unit (Π) is exemplified by the monomer described in the paragraph [〇〇43] of International Publication No. 20〇7/1 16664. Further, the structural unit (II) having a cyclic carbonate structure is exemplified by a structural unit represented by the following formula. In the above formula, Rei is a hydrogen atom or a methyl group. -27- 201219972 [Chem. 1 5] RC1 RC1 RC1 RC1 RC1 RC1

In the [A] polymer, the content of the structural unit (II) is preferably more than 10 mol%, more preferably 30 mol%, based on the total structural unit constituting the [A] polymer. %~6 0 mole%. Further, [A] polymer may have one or more structural units (Η) of -28-201219972. Further, the [A] polymer may contain the above structural unit (〇 and/or other structural units other than (11). [Other structural units] The structural units other than the above structural units (I) and/or (II) are listed as For example, it is derived from adamantyl-1-(meth)acrylate, 3-methyladamantan-1-yl (meth)acrylate, 3-ethyladamantan-1-yl (meth)acrylate, 3-Hydroxyadamantan-1-yl (meth)acrylate, 3,5-dihydroxyadamantan-1-yl (meth)acrylate, 3-cyanosadamantane-1-(meth)acrylate Base ester, 3-carboxy-n-Dragon-1-yl (meth)acrylate, 3,5-dicarboxyadamantan-1-yl (meth)acrylate, 3-carboxy-5-hydroxy (meth)acrylate A structural unit of a monomer such as adamantyl-1-yl ester or a 3-methoxycarbonyl-5-hydroxyadamantan-1-yl (meth)acrylate, etc. The radiation sensitive resin composition used in the present invention The content of the [A] polymer contained in the solid component (component of the solvent removal) is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more. [A] The content of the polymer falls within the above range, and the formability of the resist pattern can be further improved. <[A] Synthesis method of polymer> [A] The polymer can be, for example, a radical polymerization initiator, The monomer corresponding to each specific structural unit is polymerized in a suitable solvent. The synthesis method is exemplified by, for example, adding a solution of a monomer and a radical initiator to the reaction solvent or a method of performing a polymerization reaction in a solution of a monomer, and a method of performing a polymerization reaction by separately dropping a solution containing a monomer and a solution containing a radical initiator in a solution containing a reaction solvent or a monomer. The radical polymerization initiators used are exemplified by azobisisobutyronitrile (AIBN), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2' - azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), etc. These radical initiators can be used alone or in combination. The solvent used in the above polymerization is exemplified by the following: n-pentane, n-hexane, n-heptane, n-octane, orthoquinone Alkane such as alkane or n-decane; cycloalkane such as cyclohexane, cycloheptane, cyclooctane, decahydronaphthalene or norbornane; aromatic such as benzene, toluene, xylene, ethylbenzene or cumene Hydrocarbons; halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene; ethyl acetate, n-butyl acetate, isobutyl acetate, propionate Saturated carboxylic acid esters such as esters; ketones such as acetone, 2-butanone, 4-methyl-2-pentanone, 2-heptanone; tetrahydrofuran, dimethoxyethane, diethoxyethane The ether 1 is an alcohol such as methanol, ethanol, 1-propanol, 2-propanol or 4-methyl-2-pentanol, etc. These solvents may be used singly or in combination of two or more. -30- 201219972 The reaction temperature in the above polymerization is usually 4 (about TC~15 〇 °C), preferably 50 ° C to 120 ° C. The reaction time is 1 hour to 48 hours, preferably 1 Hour ~ 24 hours ° [A] The weight average molecular weight (Mw) of the polymer obtained by gel permeation chromatography (GPC) is preferably 1, 〇〇〇~1〇〇, 〇 Preferably, it is from 1,000 to 50,000, preferably from 1,000 to 30,000. By making the Mw of the [eight] polymer fall within the above range, the resistive solvent used as the photoresist is sufficient. Solubility, and dry etching resistance or photoresist pattern cross-sectional shape is improved. [A] The ratio of the Mw of the polymer to the polystyrene-converted number average molecular weight (?η) measured by the GPC method is usually (Mw/Mn). It is 1 to 3, preferably 1 to 2. <[B]acid generator> [B] The acid generating system generates an acid by exposure, and the acid dissociates the acid dissociable group present in the [A] polymer. As a result, the [A] polymer is poorly soluble in the developer containing the organic solvent. The form of the [B] acid generator in the composition may be in the form of a compound as described later (hereinafter also The "[B] acid generator" may be a form in which an anion or a cation is partially incorporated as a polymer, or a mixture of the two forms. The [B] acid generator used in the present invention contains a cation. And an anion having an alicyclic group, and the atomic ratio (F/C) of the fluorine atom to the carbon atom of the anion is 0.1 or more and 0.5 or less. By making the anion of the [B] acid generator have an alicyclic group, [B] The compatibility of the acid generator with the resin or the suitability of the composition - 31 - 201219972. Further, by making the atomic ratio (F/C) of the fluorine atom to the carbon atom in the anion 0.1 Above 0.5 or less, the [B] acid generator is not locally localized in the vicinity of the surface of the photoresist film but is uniformly dispersed. By thus uniformly dispersing the [B] acid generator in the photoresist film, the photoresist film can be suppressed. The surface acid is excessively generated, and the deprotection reaction of the specific polymer at the outermost surface of the photoresist film can be suppressed, and as a result, the occurrence of the wrong contact hole can be prevented. [B] The cation contained in the acid generator is exemplified by, for example, a phosphonium cation. Thiophene cation, ammonium cation, scale cation Among the cations, a phosphonium cation and a salivary cation are preferred, and a cation represented by the following formula (B-pc) is preferred, and a triphenylphosphonium cation is preferred. 1 6

Rpc1 ΛΗ (B-pc) S-RP®3 RPC3 (In the formula (B-pc), RPel is a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. Or an alkoxycarbonyl group having 2 to 11 carbon atoms, Rpe2 is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkanesulfonyl group having 1 to 10 carbon atoms, and each of Rpe3 is independently a carbon number. An alkyl group of 1 to 10, a phenyl group or a naphthyl group, and further, two Rpe3 groups may be bonded to each other to form a divalent group having 2 to 10 carbon atoms, t represents an integer of 0 to 2, and r represents an integer of 0 to 10). -32- 201219972 [B] The anion contained in the acid generator has an alicyclic group, and the atomic ratio (F/C) of the fluorine atom to the carbon atom contained in the anion is 0.1 or more 〇·5 or less, wherein (F/C) is preferably 0.1 or more and 0.4 or less, more preferably 0.1 or more and 0.3 or less. The anion of the [B] acid generator is preferably represented by the following formula (1). [化1 7] / R&quot;

(In the formula (1), R1 is a monovalent organic group having a monocyclic or polycyclic alicyclic group, η is 1 or 2, and Rn&amp; Rf2 are each independently a hydrogen atom, a fluorine atom or a carbon number of 1 to 4. Fluorinated alkyl group, except when Rfl&amp; Rf2 is a hydrogen atom. When Rfl and Rf2 are plural, the complex number 11〃 and Rf2 may be the same or different). In the above formula (1), the monovalent organic group having an alicyclic group represented by R1 is exemplified by a monovalent alicyclic hydrocarbon monovalent hydrocarbon group having a cycloalkane skeleton such as cyclopentane or cyclohexane. A polycyclic alicyclic group monovalent hydrocarbon group having a bridged skeleton such as an adamantane skeleton or a norbornane skeleton. The monovalent hydrocarbon group may, for example, be at least one hydrogen atom having a chain hydrocarbon group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group or an octyl group, and the above-mentioned alicyclic ring. a group substituted by a formula. Further, it is exemplified by a combination of one or more groups selected from the group consisting of an oxygen atom, a sulfur atom, an ether group, an ester group-33-201219972, a carbonyl group, an imine group, and a guanamine group. . In the above formula (1), the fluorinated alkyl group having 1 to 4 carbon atoms is exemplified by, for example, a fluorinated methyl group, a fluorinated ethyl group, a fluorinated n-propyl group, an fluorinated isopropyl group, a n-butyl fluoride group, Third butyl and the like. The anion is exemplified by, for example, a norbornane derivative, an adamantane derivative, a deoxycholate, a cholinate, etc., and the above (F/C) is 0.1 or more and 5 or less. By. The anion of the above [Β] acid generator is represented by the following formulas (2) to (5) and (8) to (25), and it is more preferable to use the following formulas (2) to (5). Indicates an anion. Further, "Me" in the formula represents a methyl group. [化1 8]

[化1 9]

[化2 0]

-34- 201219972 【化2 1】

O F F (8)

O F F (10)

(13)

(14)

S03 -35- (21 ) (20) 201219972

[B] The atomic ratio (F/C) of the fluorine-containing atom to the carbon atom in the anion of the acid generator can be determined by measuring &quot;C-NMR, iH-NMR, and IR spectroscopy; It is well free of aromatic groups. By increasing the transmissivity of the ArF excimer laser in the photoresist coating by making the anion free of aromatic groups', the light is enhanced by irradiating a uniform ArF excimer laser from the surface of the photoresist film to the vicinity of the photoresist substrate. The rectangular shape of the resistance pattern. Specific examples of the [B] acid generator: The onium salt is exemplified by, for example, triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, three Phenylhydrazine 2_bicyclo[22•丨]heptane-2_yl_ 1,1_difluoroethane sulfonate '4-cyclohexylphenyldiphenylfluorene 2-bicyclo[2.2.1]g-2 -yl-l,i,2,2-tetrafluoroethanesulfonate, 4-methanesulfonylphenyldiphenylphosphonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2 , 2-tetrafluoroethane sulfonate, diphenyl sulfonium 1,1,2,2-tetrafluoro-6-(1·adamantanecarbonyloxy)-hexane-i-sulfonate and triphenyl毓2-adamantyl- oxime, ι_difluoroethane sulfonate, and the like. Among these -36-201219972, preferably triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2 -bicyclo[2.2.1]hept-2-yl-1,1-difluoroethanesulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-6-(1-adamantanecarbonyloxy )·Hex-1-sulfonate and triphenylsulfonium 2-adamantyl-l,1-difluoroethanesulfonate. The tetrahydrothiophene key salt is exemplified by, for example, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene key 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetra Fluoroethanesulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophene 2-2-cyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoro Ethane sulfonate and (3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethyl Alkane sulfonate and the like. The onium salt is exemplified by, for example, diphenylphosphonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate and bis(4-tert-butylphenyl).鍈2-Bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethane sulfonate. These [B] acid generators may be used singly or in combination of two or more. Further, a sulfonium imine compound known as another acid generator, a halogen-containing compound, a diazoketone compound or the like can be used. The content of the [B] acid or the product contained in the solid component (the component for removing the solvent) of the radiation-sensitive resin composition used in the present invention is preferably 5% by mass or more and 10% by mass. /. Hereinafter, it is more preferably 8 mass% or more and 9 mass% or less. By setting the content of the [B] acid generator to the above range, a sufficient acid can be generated at the time of exposure. In particular, the amount of use of the [B] acid generator in the case of an acid generator is usually 0.1 part by mass with respect to 100 parts by mass of the [A] polymer from the viewpoint of sensitivity and developability of the photoresist. The above 15 parts by mass or less is preferably 3 parts by mass or more and 15 parts by mass or less, more preferably 5 parts by mass or more and -37 to 201219972 12 parts by mass or less. In this case, when the amount of the [B] acid generator is less than 0.1 part by mass, the sensitivity and the developing property tend to be lowered. On the other hand, when it exceeds 15 parts by mass, the radiation is transparent. The tendency to decrease is difficult to obtain the desired photoresist pattern. <[C] Polymer> [C] The polymer is a polymer having a fluorine atom content higher than that of the [Α] polymer. The radiation sensitive resin composition used in the photoresist pattern forming method has the characteristics of water repellency of the [C] polymer in the film by containing the [C] polymer and forming the photoresist film. Its distribution is localized to the tendency of the vicinity of the surface of the photoresist film. Therefore, it is preferable to suppress the acid generator or the acid diffusion controlling agent from being dissolved in the liquid immersion medium during the immersion exposure. Further, by utilizing the water-repellent characteristics of the [C] polymer, the contact angle of the photoresist film and the liquid immersion medium can be controlled within a desired range, and the occurrence of bubble defects can be suppressed. Further, the back contact angle of the photoresist film and the liquid immersion medium can be increased, and the scanning exposure can be performed at a high speed without leaving the water droplets remaining. Here, the [C] polymer is not particularly limited as long as it has the above properties, and when the fluorinated alkyl group is preferred, the [C] polymer has a fluorinated alkyl group in the structure, and the above characteristics can be further improved. The [C] polymer in the present invention is formed by polymerizing a monomer containing fluorine in one or more structures. The fluorine-containing monomer in the structure is exemplified by a fluorine atom in the main chain, a fluorine atom in the side chain, and a fluorine atom in the main chain and the side chain. The monomer having a fluorine atom in the main chain is exemplified by, for example, an α-fluoroacrylate compound, an α-trifluoromethacrylate compound, a β-fluoroacrylate compound, a -38-201219972 β-trifluoromethacrylate compound, An α,β-fluoroacrylate compound, an α,β-trifluoromethacrylate compound, a compound in which one or more hydrogens of a vinyl moiety are substituted with fluorine or a trifluoromethyl group, or the like. As the monomer having a fluorine atom in the side chain, for example, a side chain in which an alicyclic hydrocarbon compound such as norbornene is a fluorine or a fluoroalkyl group or a derivative thereof, a fluoroalkyl group of acrylic acid or methacrylic acid or a derivative thereof The ester compound of the substance, the side chain of one or more olefins (the site containing no double bond) is fluorine or a fluoroalkyl group or a derivative thereof. Further, the monomer having a fluorine atom in the main chain and the side chain is exemplified by, for example, α-fluoroacrylic acid, β-fluoroacrylic acid, α,β-fluoroacrylic acid, α-trifluoromethacrylic acid, β-trifluoromethacrylic acid. An ester compound of a fluoroalkyl group such as α,β-trifluoromethacrylic acid or a derivative thereof, or a side chain of a compound in which one or more vinyl groups are substituted with fluorine or a trifluoromethyl group, or the like, is fluorinated or halothane. The group or a substituent thereof is substituted by one or more kinds of hydrogen bonded to a double bond of the alicyclic olefin compound by a fluorine atom or a trifluoromethyl group, and the side chain is a fluoroalkyl group or a derivative thereof. Further, the alicyclic olefin compound is a compound in which a part of the ring is a double bond. In the present invention, the structural unit to which fluorine is imparted to the [C] polymer is not limited to the above, but a structural unit represented by the following formula (2 1 ) (hereinafter referred to as "structural unit (1)") is preferably used. [Chemical 2 3] R3

-39- 201219972 In the above formula (21), R3 represents hydrogen, a methyl group or a di-gas methyl group; A represents a linking group, and R4 is a linear or branched carbon group having 1 to 6 carbon atoms containing at least one or more fluorine atoms. An alkyl group or a carbon number 4 to 20 one-valent alicyclic hydrocarbon group or a derivative thereof. In the formula (2 1 ), A represents a linking group, and examples thereof include a mono-, an oxygen atom, a sulfur atom, a carbonyloxy group, an oxycarbonyl group, a decylamino group, a sulfonylamino group, and a urethane group. Preferred monomers for obtaining the above structural unit (1) are, for example, trifluoromethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and perfluoroethyl (meth)acrylate. , (meth)acrylic acid perfluoro-n-propyl ester, (meth)acrylic acid perfluoroisopropyl ester, (meth)acrylic acid perfluoro-n-butyl ester, (meth)acrylic acid perfluoroisobutyl ester, (meth)acrylic acid Perfluorotributyl ester, 2-(1,1,1,3,3,3-hexafluoropropyl) (meth)acrylate, 1-(2,2,3,3, (meth)acrylate 4,4,5,5-octafluoropentyl)ester, (meth)acrylic acid perfluorocyclohexylmethyl ester, (meth)acrylic acid 1-(2,2,3,3,3-pentafluoropropene Base) ester '(meth)acrylic acid 1-( 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,1〇-heptadecane Sulfhydryl, vinegar, 1-(5-trifluoromethyl-3,3,4,4,5,6,6,6-octafluorohexyl) vinegar, 2-(meth)acrylic acid 2-three Fluoromethyl-2-hydroxy-trifluoro-4-pentyl ester and the like. The above [C] polymer may contain only one type of the structural unit (1), or may contain two or more types. When the content ratio of the structural unit (1) is 1 〇〇 mol % of all the structural units in the [C] polymer, 'usually 5 mol% or more, preferably 10 mol% or more, more preferably It is more than 5 moles. When the content of the structural unit -40-201219972 (1) is less than 5 mol%, the retreat contact angle of 70 degrees or more cannot be achieved, and the elution of the self-resistance film such as an acid generator cannot be suppressed [C The polymer may contain, in addition to the structural unit containing fluorine in the above structure, one or more structural units having, for example, an acid dissociable group for controlling the dissolution rate of the developing solution, or a lactone skeleton or a hydroxyl group. a structural unit such as a carboxyl group, or a structural unit having an alicyclic compound, or a "other structural unit" derived from a structural unit derived from an aromatic compound for suppressing light scattering by reflection from a substrate. The acid-dissociable group in the other structural unit may be the same as the structural unit (I) of the [A] polymer (hereinafter also referred to as "structural unit (2)"). The structural unit (2) is preferably, for example, 2-methyladamantane-2-(meth)acrylate, 2-ethyladamantan-2-yl (meth)acrylate, or (meth)acrylic acid. 2-Methylbicyclo[2.2.1]hept-2-yl ester, (methyl)propionic acid 2·ethylbicyclo[2. ^heptyl-2,yl ester, yttrium (meth)acrylate_(bicyclo[2.2.1]hept-2-yl)-indole_methylethyl ester, (meth)acrylic acid 1-(金刚院-1- -1 - methyl ethyl ester, 1-methyl-1-cyclopentyl (meth)acrylate, 1-ethyl-1-cyclopentyl (meth)acrylate, (methyl) propyl Bar acid 1-methyl·丨_cyclohexyl ester, (meth)acrylic acid 丨_ethyl-i_cyclohexyl ester, and the like. For example, the same as the structural unit (Π) of the [A] polymer (hereinafter also referred to as "structural unit (3)") can be used as the inner vinegar skeleton. The alicyclic compound may be, for example, a structural unit represented by the following formula (22) -41 - 201219972 (hereinafter also referred to as "structural unit (4)"). [Chem. 24] R5

(22) In the above formula (22), R5 represents a hydrogen atom, a methyl group or a trifluoromethyl group. Y is an alicyclic hydrocarbon group having 4 to 20 carbon atoms. The alicyclic hydrocarbon group having a carbon number of 4 to 20 represented by Y in the above formula (22) is exemplified by, for example, cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2. 2] alicyclic ring of octane, tricyclo[5.2.1.02,6]decane, tetracyclo[6.2.1.13,6.02,7]dodecane, tricyclo[3.3.1.13,7]decane a hydrocarbon group formed by a family ring. The cyclohexane-derived alicyclic ring may have a substituent, and the substituent is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methyl. One or more or one or more substitutions of a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms such as a propyl group and a third butyl group. These are not limited to those substituted with such an alkyl group, and may be substituted with a hydroxy group, a cyano group, a hydroxyalkyl group having 1 to 1 carbon number, a carboxyl group or an oxygen atom. Preferred monomers for obtaining the structural unit (4) are (meth)acrylic acid-bicyclo[2.2.1]hept-2-yl ester, (meth)acrylic acid-bicyclo[2.2.2]oct-2-yl ester , (meth)acrylic acid, tricyclo[5.2.1.02'6]non-7-yl ester, (meth)acrylic acid-tetracyclo[6.2.1.13,6.〇2,7]dodecane-9-yl Ester, (meth)acrylic acid-tricyclo[3.3.1.I3'7]non-1-yl ester, (meth)acryl-42-201219972 acid-tricyclo[3.3.1.I3'7]癸- 2-Base ester and the like. Further, preferred monomers derived from an aromatic compound (hereinafter referred to as "structural unit (5)") are exemplified by, for example, styrene, α-methylstyrene, 2-methylstyrene, and 3-methyl group. Styrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-(2-tert-butoxycarbonylethyloxy) Styrene, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2-hydroxy-α-methylstyrene, 3-hydroxy·α-methylstyrene, 4-hydroxy-α-A Styrene, 2-methyl-3-hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxystyrene, 2-methyl-4-hydroxystyrene, 3- Methyl-4-hydroxystyrene, 3,4-dihydroxystyrene, 2,4,6-trihydroxystyrene, 4-tert-butoxystyrene, 4-tert-butoxy-α-A Styrene, 4-(2-ethyl-2-propoxy)styrene' 4-(2-ethyl-2-propoxy)-α-methylstyrene, 4-(1·ethoxy Ethyl ethoxy) styrene, 4-(1-ethoxyethoxy)-α-methylstyrene, phenyl (meth)acrylate, benzyl (meth)acrylate, decene, 5- Basene, 1-vinylnaphthalene, 2-vinylnaphthalene, 2-hydroxy-6-vinylnaphthalene, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, (A) Base) 1-naphthylmethyl acrylate, 1-decyl (meth) acrylate, 2- decyl (meth) acrylate, 9- decyl (meth) acrylate, 9-(meth) acrylate Mercapto methyl ester, 1-vinyl perylene, and the like. In the [c] polymer of the present invention, the "other structural unit" represented by the structural unit (2), the structural unit (3), the structural unit (4), and the structural unit (5) may contain only one species, and It can contain two or more types. The content ratio of the other structural unit is generally less than 80% by mole, preferably less than 75% by mole, more preferably all of the structural units in the [c] polymer as 1〇〇莫-43-201219972 耳%, more preferably It is 70% or less. Further, the [C] polymer may contain structural units other than the structural units (1) to (5) within the range not impairing the effects of the present invention. Further, the fluorine content (% by mass) of the [A] polymer and the [C] polymer can be determined by measuring 13C-NMR, W-NMR, and IR spectra. The content of the [C] polymer contained in the solid content (the solvent-removing component) of the radiation-sensitive resin composition used in the present invention is preferably 1% by mass or more and 10% by mass or less, more preferably 1.5. The mass% or more is 8% by mass or less, and more preferably 2% by mass or more and 3% by mass or less. By making the content of the [C] polymer within the above range, the formation pattern of the photoresist pattern in the immersion exposure can be further improved. [The synthesis method of the [C] polymer] [c] The polymer can be freely used, for example, by using The base polymerization initiator is produced by polymerizing a monomer corresponding to each specific structural unit in a suitable solvent. The radical initiator and solvent used in the above polymerization are exemplified by, for example, the same radical initiators and solvents as those enumerated in the synthesis method of the [A] polymer. The reaction temperature in the above polymerization is usually preferably from 40 ° C to 150 ° C, more preferably from 50 ° C to 120 t. The reaction time is usually from 1 hour to 48 hours, more preferably from 1 hour to 2 hours. [〇] The polymer 1^ is preferably 1, 〇〇〇~5〇, 〇〇〇, more preferably 1, 〇〇〇~ 30,000, preferably 1,000 to 10,000. [(:]Polymer]^ When you have not reached 1,000 -44- 201219972, you cannot get enough front contact angle. On the other hand, when Μλυ exceeds 50,0 0, there will be a photoresist. The tendency of the developing property to decrease. [C] The ratio of Mw to Μη of the polymer (Mw/Mn) is usually from 1 to 3, preferably from 1 to 2. <Optional composition> The composition except the [A] polymer In addition to the [B] acid generator and the [C] polymer, other optional components may be contained within a range that does not impair the effects of the present invention. Other optional components may contain, for example, an acid diffusion controlling agent, a solvent, and [B] acid. An acid generator other than the body, a surfactant, a compound containing an alicyclic skeleton, a sensitizer, etc. [Acid diffusion control body] The acid diffusion control body is an acid which controls the acid generation from the [B] acid generator due to exposure. The diffusion phenomenon in the photoresist film exerts an effect of suppressing a poor chemical reaction in the unexposed region, further improves the storage stability of the obtained radiation-sensitive resin composition, and further improves the resolution as a photoresist while suppressing the self-resistance Photoresist diagram caused by changes in exposure time to exposure processing The line width variation of the type can obtain excellent process stability. Moreover, the form of the acid diffusion control body in the composition can be in the form of a free compound, or can be incorporated as a part of the polymer. The acid diffusion controlling agent is exemplified by, for example, an amine compound, a guanamine group-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, etc. -45- 201219972 The amine compound is exemplified by, for example, a mono(cyclo)alkyl group. Amines; di(cyclo)alkylamines; tri(cyclo)alkylamines; substituted alkylanilines or derivatives thereof; ethylamine, N,N,N',N'-tetramethyl Diamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4,-diaminodiphenyl ether, 4,4'-diamine Benzophenone, 4,4,-diaminodiphenylamine, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-amine Phenyl)propane, 2-(4-aminophenyl)-2-(3.hydroxyphenyl)propane, 2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane, 14 _bis 0 aminophenyl)-1-methylethyl)benzene, 1,3 - bis(ι·(4-aminophenyl)-1-methylethyl)benzene, bis(2-dimethylaminoethyl)ether, bis(2-diethylaminoethyl)ether, 1 - (2-hydroxyethyl)-2 _imidazolidine, 2-quinoxaline alcohol, hydrazine, hydrazine, hydrazine Ν, Ν'-肆 (2-hydroxypropyl) ethylenediamine, ν, Ν, Ν' , Ν,,, ν,, _ pentamethyldiethylenetriamine, etc. As the compound containing a guanamine group, for example, an amine group compound containing ruthenium-tert-butoxycarbonyl group such as ruthenium-t-butoxyalkyl-4-hydroxypiperidine, formazan, hydrazine-methylformamide , Ν, Ν - dimethylformamide 'acetamide, 1 methyl acetamide, hydrazine, hydrazine - dimethyl acetamide, acetamide, benzamide, vaginal ketone, hydrazine - Methyl pyrrolidone, hydrazine-ethenyl buckhamamine, iso-uric acid tris(2-hydroxyethyl) ester, and the like. Urea compounds are exemplified by, for example, urea, methyl urea, 1,1-dimethylmethyl, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea , base sulfur veins, etc. The nitrogen-containing heterocyclic compound is exemplified by, for example, an imidazole; a pyridine; D is a hydrazine: pyrazine, a pyrazole, a pyridazine, a quinazoline, an anthracene, a pyrrolidine, and a N-di-butyl-46-201219972 oxycarbonyl group. Pyrrolidine, piperidine, piperidine ethanol, 3-piperidinyl-1,2-propanediamine, morpholine, 4-methylmorpholine, ;-(4-morpholinyl)ethanol, 4-ethylhydrazine Porphyrin, 3-(N-morpholinyl)-12-propanediol, N-cyclohexylcarbonyloxymorpholine, 1,4-dimethylpiperazine, indole, 4-diazabicyclo[2.2.2] Octane and so on. Further, as the acid diffusion controlling agent, a weak photocracking base can be used by exposure. An example of a photodisintegrating base is a key salt compound which is controlled by exposure decomposition and which is toxic to acid diffusion. The key salt compound is exemplified by an onium salt compound represented by the following formula (23), an onium salt compound represented by the following formula (24), and the like. Among them, triphenylsulfonium salicylate is preferred. [Chemical 2 5 ] Alcoholic acid loss as shown R6

(24) (Eq. (23) ^ (24) Φ, R6~R10 are each independently a hydrogen atom, a courtyard atom, a thiol or a dentate atom, and a formula (η) and a formula ( ), Z- OH., WO·, RU-S〇3- or an anion represented by the following formula ((1), but R11 is an alkyl group, an aryl group or an alkylaryl group). 2 4 Table-47-201219972 [Chem. 2 6] (25) Ο (In the formula (25), R12 is a linear or branched alkyl group having 1 to 12 carbon atoms or a linear chain having 1 to 12 carbon atoms which may be partially or wholly substituted by a fluorine atom. a branched or branched alkoxy group, u is an integer of 0 to 2.) The acid diffusion controlling agents may be used singly or in combination of two or more. The acid diffusion controlling agent is contained in an amount of 100 parts by mass relative to the [A] polymer. When the total amount is more than 5 parts by mass, the sensitivity as a photoresist tends to be lowered. [Solvent] The composition usually contains a solvent. The solvent may be at least polymerized as described above [A]. The solvent, the [B] acid generator, the [C] polymer, and the optional component to be added are not particularly limited. The solvent is exemplified by, for example, an alcohol solvent, an ether solvent, a ketone solvent, or a guanamine solution. And an ester solvent, a mixed solvent, etc. The specific example of a solvent is the same as the above-mentioned organic solvent. These are preferably propylene glycol monomethyl ether and cyclohexanone. These solvents can be used individually. Two or more types are used. [[B] Acid generator other than acid generator] -48- 201219972 The composition may also contain an acid generator other than the [B] acid generator insofar as the effects of the present invention are not impaired. The acid generators are exemplified by, for example, a key salt compound other than the [B] acid generator, a sulfonimide compound, a halogen-containing compound, a diazoketone compound, etc. The key salt compound is exemplified by, for example, a phosphonium salt (containing tetrahydrogen). a thiophene key salt, a phosphonium salt, a squara salt, a diazo salt, a pyridyl salt, etc. The sulfonium salt is exemplified by, for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluorobutane sulfonate, Triphenylsulfonium perfluoro-n-octane sulfonate, triphenyl camphorsulfonate, 4-cyclohexylphenyldiphenylphosphonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylphosphonium Fluorine butane sulfonate, 4-cyclohexylphenyldiphenylphosphonium perfluorooctane sulfonate, 4-cyclohexyl Phenyldiphenyl camphorsulfonate, 4-methanesulfonylphenyldiphenylphosphonium trifluoromethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium nonafluorobutanesulfonic acid a salt, 4-methanesulfonylphenyldiphenylphosphonium perfluorooctanesulfonate, 4-methanesulfonylphenyldiphenylcamphorsulfonate, etc. The tetrahydrothiophene key salt is exemplified as 1 - (4-n-butoxynaphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene hexafluoro-n-butane sulfonate Acid salt, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene-perfluoro- n-octane sulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene Camphorsulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophene trifluoromethanesulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophene Nonafluoro-n-butane sulfonate, 1-(6-n-butoxynaphthyl)tetrahydrothiophene-perfluoro- n-octane sulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrogen Thiophene citrate, 1-(3,5-dimethyl-4-transphenyl)tetrahydrothiophene iron difluoro-49- 201219972 methane sulfonate, 1-(3,5-dimethyl -4-hydroxyphenyl) four Thiophene nonafluoro-n-butane sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene-perfluoro- n-octane sulfonate, 1-(3,5-dimethyl Alkyl-4-hydroxyphenyl)tetrahydrothiophene iron camphorsulfonate and the like. The onium salt is exemplified by, for example, diphenyliodonium trifluoromethanesulfonate, diphenylphosphonium nonafluorobutanesulfonate, diphenylphosphonium perfluorooctanesulfonate, diphenyl-locked camphorsulfonic acid. Salt, bis(4-tert-butylphenyl) benzotrifluoromethanesulfonate, bis(4-t-butylphenyl)- town nonafluoro-n-butane sulfonate, bis(4-tert-butyl Phenyl) fluorene perfluoro-n-octane sulfonate, bis(4-t-butylphenyl)-anthraquinone sulfonate, and the like. The sulfonimide compound can be exemplified by, for example, N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenide, N-(nonafluoro-n-butane) Sulfomethoxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenine, N-(perfluoro-n-octanesulfonyloxy)bicyclo[2.2.1]hept-5- Aceene-2,3-dicarboxylimenine, N-(2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy)bicyclo[2.2. 1]hept-5-ene-2,3-dicarboxyarsenine, N-(2-(3-tetracyclo[4.4.0.12'5·]7'1 Q]dodecyl]-1,1 -difluoroethanesulfonyloxy)bicyclo[2·2·1]hept-5-ene-2,3-dicarboxylimenine, N-(camanosylsulfonyloxy)bicyclo[2.2.1] Hept-5-ene-2,3-dicarboxylimine, etc. Further, these other acid generators may be used in combination of one or more types. [Surfactant] The surfactant may exhibit improved coatability, streaking, and display. The effect of the like, etc. As for the surfactant, for example, polyoxyethylene lauryl ether, poly-50-201219972 oxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octyl phenyl ether, poly Oxyethylene n-decyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol Nonionic surfactants such as distearate are also exemplified by the following trade names KP341 (Shin-Etsu Chemical Co., Ltd.), POLYFLOW No. 75, POLYFLOW No. 95 (above, Kyoei Chemical Co., Ltd.), EF TOP EF301, EF TOP EF303, EF TOP EF3 52 (above TOHCHEM PRODUCTS), MEGAFAC FI 71, MEGAFAC F173 (above is Dainippon Ink Chemical Industry Co., Ltd.), FLORARD FC430, FLORARD FC431 (above Sumitomo 3M), ASAHI GUARD AG710, SURFLON S-3 82, SURFLON SC-10 1 , SURFLON SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-106 (above, Asahi Glass), etc. The agent may be used singly or in combination of two or more kinds. [Compound containing an alicyclic skeleton] The compound containing an alicyclic skeleton exhibits effects of improving dry etching resistance, a resist pattern shape, and adhesion to a substrate. The compound containing an alicyclic skeleton is exemplified by: adamantane derivatives such as 1-adamantanecarboxylic acid, 2-adamantanone, and 1-adamantanecarboxylic acid tert-butyl ester; tert-butyl deoxycholate; Deoxycholate esters such as tributoxycarbonyl methyl deoxycholate and 2-ethoxyethyl deoxycholate; tert-butyl lithochate, third butoxycarbonyl methyl lithate, lithocholic acid -51 - 201219972 2-ethoxyethyl esters and other cholinates; 3-[2-hydroxy-2,2-bis(trifluoromethyl)ethyl]tetracyclo[4.4.0.12'5.17'1 ( )] Dodecane, 2-hydroxy-9-methoxycarbonyl-5-oxo-4-oxa-bicyclo[4.2.1.03'7] brothel, and the like. These compounds having an alicyclic skeleton may be used singly or in combination of two or more. [Sensitizer] The sensitizer exhibits an effect of increasing the amount of [B] acid generator produced, and exhibits an effect of improving the "apparent sensitivity" of the composition. The sensitizers are listed, for example, as oxazoles, acetophenones, benzophenones, naphthalenes, anthraquinones, diacetyl quinones, eosin, rose red, pyrenes, anthraquinones. , phenothiazines and the like. These sensitizers may be used singly or in combination of two or more. <Preparation of Radiation-Sensitive Resin Composition> The composition can be obtained by mixing [A] polymer, [B] acid generator, [C] polymer, and other optional components in a specific ratio, for example, in an organic solvent. modulation. Further, the composition can be used in a state of being dissolved or dispersed in a suitable organic solvent. [Examples] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited by the examples. Further, in the examples and comparative examples, "parts" and "%" are quality standards unless otherwise specified. -52- 201219972 The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined by using a GPC column (TOSOH, 2 G2000HXL, 1 G3000HXL, 1 G4000HXL) using a gel permeation chromatograph under the following conditions. (GPC) 'Measured with monodisperse polystyrene as a standard substance.

Column temperature: 40 °C Solvent: tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) Flow rate: 1.0 mL/min Sample concentration: 1.0% by mass Sample injection amount · · 1 〇〇μ L Detector: Differential refractometer 1H- NMR analysis and 13 C-NMR analysis were carried out using a nuclear magnetic resonance apparatus (Sakamoto Electronics Co., Ltd., JNM-EX270). The [A] polymer, [B] acid generator, [C] polymer, acid diffusion controlling agent and solvent used in the preparation of the composition are as follows. The monomers used in the synthesis of the following [A] polymer and the [C] polymer described later are shown below. [化 2 7]

(M·1) (M-2) (M-3) (M-4) -53- 201219972

(Μ-15) <[Α] Polymer Synthesis> As for the [A] polymer, the following polymers (A-1) to (A-8) were used [Synthesis Example 1] -54 - 201219972 <Polymer (Al)> The monomer (M-1) 12.936 (50 mol%) represented by the above formula and the monomer (M-8) 17.07 g (50 mol%) were dissolved in 60 g of 2-butanone, followed by A 0.50 g preparation solution of azobisisobutyronitrile was injected. Next, a 200 mL three-necked flask in which 30 g of 2-butanone was injected was blown with nitrogen for 30 minutes, and then heated to 80 ° C while stirring the reaction vessel, and a preliminarily prepared monomer solution was added dropwise over 3 hours using a dropping funnel. . The polymerization was carried out for 6 hours starting from the start of the dropwise addition as the starting time of the polymerization. After the completion of the polymerization, the polymerization solution was cooled to 30 t or less with water cooling. Pour into 60 Og of methanol and filter the precipitated white powder. The filtered white powder was washed twice with a solution of 150 g of methanol, and then filtered and dried at 50 ° C for 17 hours to obtain a white powdery polymer (Al) (Mw = 13,000, Mw / Mn = 1.5, yield = 85%). The ratio of the structural unit derived from (M-1) / (M-8) in the polymer (A-1) was 5 0/5 0 (mole %). [Synthesis Example 2] <Polymer (A-2)> Except as shown in Table 1 below, monomers (M-2), monomers (M-3), and monomers (M-8) were used as monomers. The operation was carried out as in the above Synthesis Example 1 to obtain a polymer (A-2) (Mw = 7,000, Mw / Mn = 1.4, yield = 83%). The ratio of the structural unit derived from (M-2) / (M-3) / (M-8) in the polymer (A-2) was 15/35/5 〇 (mol%). [Synthesis Example 3] -55-201219972 <Polymer (A-3)> Except the following Table 1, the above monomers (M-3), monomers (M-6) and monomers (M-8) were used. The operation was carried out as in the above Synthesis Example 1 to obtain a polymer (A-3) (Mw = 6,000, Mw / Mn = 1.4, yield = 87%). The ratio of the structural unit derived from (M-3) / (M-6) / (M-8) in the polymer (A-3) was 60/20/20 (mol%). [Synthesis Example 4] <Polymer (A-4)> In addition to the above-mentioned monomer (M_3), monomer (M-7), and monomer (M-12) as monomers, except as shown in Table 1 below] The operation was carried out as in the above Synthesis Example 1 to obtain a polymer (A_4) (Mw = 7,000 »

Mw / Mn = 1.4, yield = 85%). The ratio of the structural unit derived from (1^-3) / (M-7) / (M-12) in the polymer (A-4) was 40/30/30 (mol%). [Synthesis Example 5] <Polymer (A-5)> The monomers (M-2), monomers (M-7) and monomers (M-10) were used as the monomers as shown in Table 1 below. Except that the above Synthesis Example 1 was operated to obtain a polymer (A_5) (Mw = 7,800 '

Mw / Mn = 1.6, yield = 80%) ° The ratio of the structural unit derived from (仏2) / (M-7) / ( ) in the polymer (A-5) is 40/10/50 (Mo Ear %) -56- 201219972 [Synthesis Example 6] <Polymer (A-6)> The above-mentioned monomer (M-3), monomer (M-7), and monomer were used as shown in Table 1 below. M-1 1 ) As a monomer, the remainder was operated as in the above Synthesis Example 1 to obtain a polymer (A_6) (Mw = 8,200 &gt;

Mw / Mn = 1.6, yield = 81%). The ratio of the structural unit derived from (M-3) / (M-7) / (M-1 1 ) in the polymer (A-6) was 40/30/30 (mol%). [Synthesis Example 7] <Polymer (A-7)> Except as shown in Table 1 below, a monomer (M-4), a monomer (M-7), and a monomer (M-9) were used as a monomer. The operation was carried out as in the above Synthesis Example 1 to obtain a polymer (A-7) (Mw = 7,900, Mw / Mn = 1.5' yield = 80%). The ratio of the structural unit derived from (M-4) / (M-7) / (M-9) in the polymer (A-7) was 30/25/45 (mol%). [Synthesis Example 8] <Polymer (A-8)> In addition to the following Table 1, the above monomers (M-5), monomers (M-7) and monomers (M-12) were used as monomers. The operation was carried out as in Synthesis Example 1 above to obtain a polymer (A·8) (Mw = 7,3 00 &gt;

Mw / Mn = 1.5, yield = 78%). The ratio of the structural unit derived from (M- -57-201219972 5 ) / ( M-7 ) / ( M-12 ) in the polymer (A-8) is 3 0/25/45 (mole 0/〇) ). [Table 1] [A] Polymer Monomer Polymerization Starter Physical Property Unit 0) Structure 骂 [Position (Π) Other structural unit type mm Quantitative amount of spectroscopy (Mole%) Surface ration (Mole %) Formulation amount %) Mw Mw/Mn Yield (%) Structure content (mol%) _1 A-1 MI 50 Μ-8 50 — — 2 13 side 1.S 85 50/50 2 Α·2 M-2/M-3 15/35 Μ-8 60 — — 5 vm 1.4 S3 15/35/&amp;0 Synthesis Example 3 Α-3 M-3 60 Μ-6/Μ-8 20/ 20 one - δ 6 Na 1.4 37 60/20/2U Synthetic M4 Α-4 Μ-3 40 30 Μ-7 30 5 7.001&gt; \Λ 3$ 4〇/30/$0 Synthesis Example 5 AS Μ-2 40 MHO 50 Μ-7 10 S Λ&amp;00 SO 40/10/SO 锣成锣6 Α-6 Μ-3 40 Μ-11 30 U-7 30 δ 8.200 t.6 81 40/30/30 7 Α-7 Μ -4 30 W-9 45 Μ-7 25 5 7靡Ϊ.5 80 30/25/45 8 Α-8 Μ-5 30 M-12 45 Μ-7 2S 5 λ300 1.5 78 30/25/45 〈[ B] Acid generator> [B] The acid generator is the following (B-1) to (B-7). (B-1): triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate represented by the following formula [Chem. 2 8]

(B-2): triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1-difluoroethanesulfonate represented by the following formula -58-201219972 [Chem. 2 9]

S03 (B-3): triphenylphosphonium 2-adamantyl-1,1-difluoroethanesulfonate represented by the following formula [Chemical 3 0] f2

C, S03

(Β-3) (Β-4): triphenylsulfonium 1,1,2,2-tetrafluoro-6-(1-adamantanecarbonyloxy)-hexane-1-sulfonate represented by the following formula [化3 1]

-59 - 201219972 (B-5): Triphenylsulfonium 1,1,2,2,3,3,4,4,4-non-fluorobutanesulfonate represented by the following formula [Chemical 3 2]

B-5) W, meaning c/s〇3 F2 f2 (B-6): triphenylsulfonium 2-cyclohexylmethyloxycarbonyl-1,1,1,3,3,3- Hexafluoropropane-2-sulfonate [Chemical 3 3]

(B-6) (B-7): Triphenyl camphorsulfonate represented by the following formula -60-201219972 [Chem. 3 4]

(B-7) <Sc Synthesis of Polymer> [C] Polymer using the following polymer (c_1} and polymer (c 2 ) ° [Synthesis Example 9] <Polymer (C-1) 〉 The monomer (M-2) 21.50 § (70 mol%) and the monomer (M-13) 8.508 (30 mol%) represented by the above formula are dissolved in 2-butanone 6 〇§, followed by injection 2 2'-Azobis(isobutyronitrile) i.38g preparation solution. Then, a 2-neck flask of 30 g of 2-butanone was injected with nitrogen gas for 30 minutes, and then heated while stirring the reaction vessel to The monomer solution prepared in advance was added dropwise at 80 ° C over 3 hours using a dropping funnel. The polymerization was started for 6 hours starting from the start of the dropwise addition. After the completion of the polymerization, the solution was cooled to 30 ° with water cooling. C was poured into 600 g of methanol, and the precipitated white powder was filtered. The filtered white powder was washed twice with 150 g of methanol, and then filtered and dried at 50 ° C for 12 hours to obtain a white powder. Polymer (C -1 ) ( Mw = 7,500, Mw / Mn = 1.4, yield = 89%). The structure derived from (M_2 ) / ( M-13 ) in polymer -61 - 201219972 (cl ) The ratio of units is 7 0/30 (mol%). [Synthesis Example 10] <Polymer (C-2)> Except as shown in Table 2 below, monomers (M-2), monomers (M-14) and monomers were used. (M-15) A monomer (C-2) (Mw = 6,500, Mw/Mn = 1.5, yield = 82%) was obtained as the above-mentioned Synthesis Example 9 except for the monomer. -2) The ratio of the structural unit derived from (M_2) / ( M_14) / (M-15) is 50/40/1 0 (mole %) β [Table 2] [C] Polymer monomer - Polymerization initiation W Synthesis Example 9 Synthesis Example 10 Ugly C-1 C-2 Surface Μ-2 Μ-2 Dispensing amount of indifference %) 70 50 Type Μ-13 Μ-14 Dispensing S 谟 ear%) 30 40 Griffin- 15 Mixing amount of indifference %) 10 Dispensing S indifference %) 7 7 — Mw 7,500 0500 Mw/Mn 1.4 _ 1.5 Yield (%) 09 B2 Structure content rate (Moor 70/30 50/40/10 ([ D] Acid Diffusion Control Agent) The acid diffusion control agent uses the following (D-1) Ν-t-butoxydecyl-4-hydroxypiperidine, (D-2) triphenylsulfonium salicylate And (〇·3) Ν_cyclohexylcarbonyloxyethylmorpholine. -62- 201219972 [Chem. 3 5]

<Solvent> As the solvent, the following (^) and (E_2 E-1. propanol monomethyl acetate vinegar E-2: cyclohexanone [Example 1] <Modulation of light-ray sensitive resin composition was used. 〉 Mixed polymer (A-1) 1 part by mass, (B-1) 9, 5 parts by mass, polymer (C-1) 3 parts by mass, (D-1) 0.94 parts by weight, (E-1) 2,010 parts by mass and (E-2) 860 parts by mass, a homogeneous solution, and then filtered using a membrane filter having a pore size of 200 nm to prepare a radiation-sensitive resin composition (hereinafter, composition 1). The concentration was 5% by mass. [Examples 2 to 19] Except that the types and the amounts of the [A] polymer, the [B] acid generator, and the acid diffusion controlling agent were as shown in Table 3 below, the operation was as in Example 1. Modulation of the radiation-sensitive resin composition (hereinafter, Composition 2 to 19) ° -63 - 201219972 [Comparative Examples 1 to 6] In addition to [A] polymer, [B] acid generator, acid diffusion control agent The type and the amount of the preparation were the same as those in the following Table 3. The operation of Example 1 was carried out to prepare a radiation-sensitive resin composition (hereinafter, Compositions 20 to 25). [Table 3] [Α] Polymer [B] Producer [c] Polymer acid diffusion control agent Coating liquid surface usage amount (parts by mass) Surface usage amount (parts by mass) Turning the amount of the product) _ Use Λ Reimbursement) Example 1 ΑΗ ΟΟ ΟΟ B- 1 9.5 (Μ 3 D-1 0.94 Composition 1 贲 Example 2 B-2 9.5 C, 1 3 ΪΜ 0.94 诚 2 贲 Example 3 ύ-ζ 93 CT 3 Dt 0.94 Composition 3 a Example 4 8 -3 9.5 C-2 3 0-2 2 Composition 4 Example 5 Β^3 9.5 02 3 D~3 0.94 Composition 5 实福6 Α-2 &lt;00 Β-3 9.5 \ 3 D-2 2 Composition Example 6 Example 7 8 «3 9.5 02 3 D-3 0.94 Composition 7 Example δ Α-3 100 8-S 9.5 C-1 3 D-2 2 Composition 8 Example 9 8-4 as C- 1 3 l&gt;-2 2 Composition 9 Example 10 Α-4 100 Β-2 9,5 C-1 3 D-1 0.S4 Composition 10 Example 11 8*3 9.5 02 3 D-3 0.94 : Pulmonary 11 Example 12 Rift 5 too Β-3 as C-1 3 0-2 2 Ship 12 S Example 13 8*-4 9.5 C-1 3 D-3 0.94 Transport 13 Example 14 Α -6 100 Β-2 9.5 C-2 3 D-1 a94 broth 14 ΘExample 15 8·4 as 02 3 D-3 CX94 Composition 15 S Example 16 Α-7 100 Β-3 9.5 C-2 3 0»2 2 Composition 16 Example 17 Β-3 9.5 C-2 3 D-3 a94 Composition 17 Example 18 Λ-3 ICO Β-2 as C-1 3 D-1 0J4 Progenitor 18 Η Example 19 8-4 9.5 C-1 3 0.94 Composition 19 Comparative Example 1 AJ 100 Β-5 9.5 C- 1 3 tM 0.94 Composition 20 Comparative Example 2 Β-6 9l5 ot 3 DM 0.94 Composition 21 Comparative Example 3 Β-7 12 C-1 3 0-1 0.94 Composition 22 Comparative Example 4 Λ-7 100 Β-5 Θ .5 C-2 3 D-3 0.84 Composition 23 Comparative Example 5 β-6 9.5 C-2 3 D-3 0.94 Composition 24 Comparative Example 6 Β-7 12 C-2 3 Cl·-3 0.94 ii 25 [Example 20] <Formation of a photoresist pattern> An antireflective film forming agent (manufactured by BREWER. SCIENCE, trade name "ARC66") was spin-coated with "CLEAR TRACK Lithius Pro i" (manufactured by Tokyo Electronics Co., Ltd.). After the wafer was deposited on a 12-inch wafer, it was pre-baked (PB) at -64 - 201219972 at 205 °C for 60 seconds to form an anti-reflection film with a film thickness of 105 nm. The composition 1 obtained above was spin-coated on the substrate using "CLEAR TRACK Lithius Pro i" (manufactured by Tokyo Electronics Co., Ltd.), and pre-baked (PB) at 90 ° C for 60 seconds, and then cooled at 23 ° C. Second, thereby forming a photoresist layer having a film thickness of 100 nm. Subsequently, an ArF immersion exposure apparatus ("NSR-S610C", manufactured by NIKON Seiki Co., Ltd.) was used, and exposure was performed under the optimum focusing conditions with NA = 1.3, optical conditions of four poles. On the hot plate of the trade name "CLEAR TRACK Lithius Pro i", post-exposure baking (P EB ) was performed at 10 ° C for 60 seconds, and after cooling at 30 ° C for 30 seconds, methylpentyl group was used. The ketone was visualized as a developing solution for 30 seconds, and washed with 4-methyl-2-pentanol for 7 seconds. The spin drying was carried out at 200 rpm for u seconds, thereby forming a photoresist pattern of 48 nm hole/96 nm interval. [Examples 21 to 38, Comparative Examples 7 to 12] A photoresist pattern was formed as in Example 20 except that the coating liquid type, the pB temperature and the pEB temperature in Table 4 below were used. The evaluation results of the obtained photoresist patterns are combined with § 5 in Table 4. -65- 201219972 [Table 4] Coating liquid Sa PB PEB Sensitivity (mJ/cm2) Number of wrong contact holes (unit) [B] F/C temperature of anion of acid generator (. 〇 temperature (. 〇 Example 20 Composition 1 90 105 20 0 0.44 Example 21 Composition 2 90 105 22 0 0.22 Example 22 Composition 3 90 105 31 0 0.16 Example 23 Composition 4 90 105 31 0 0.16 Example 24 Composition 5 90 105 33 0 0.16 Example 25 Composition 6 100 115 27 0 0.16 Example 26 Composition 7 100 115 29 0 0.16 Example 27 Composition 8 100 95 29 0 0.16 Example 28 Composition 9 100 95 22 0 0.22 Example 29 10 10 115 30 0 0.22 Example 30 Composition 11 90 115 33 0 0, 16 Example 31 Composition 12 90 95 27 0 0.16 Example 32 Composition 13 90 95 23 0 0.22 Example 33 Composition 14 90 115 29 0 0.22 Example 34 Composition 15 90 115 27 0 0.22 Example 35 Composition 16 90 95 25 0 0.16 Example 36 Composition 17 90 95 26 0 0.16 Example 37 Composition 18 90 95 22 0 0.22 Example 38 Composition 19 90 95 21 0 0.22 Comparative Example 7 Composition 20 90 105 17 15 2.25 Comparative Example 8 Composition 2 1 90 105 19 3 0.55 Comparative Example 9 Composition 22 90 105 One image unresolved No result 0.00 Comparative Example 10 Composition 23 90 95 14 20 2.25 Comparative Example 11 Composition 24 90 95 15 13 0.55 Comparative Example 121 Composition 25 90 95 - Pattern unresolved no result 0.00 <Evaluation> [Sensitivity (mJ/cm2)] In the above resist pattern formation, the exposure amount (nU/cm2) is 1 (mJ/cm2) from 10 The size of the contact hole was measured by changing to 40. The exposure amount of 48 nm which is the target size was used as the sensitivity. [The number of the wrong contact holes] The evaluation was performed using the respective photoresist patterns obtained above. The evaluation was performed using a measurement manufactured by Hitachi High Technologies. SEM "CG-4000". The observation magnification was 50K times, and the number of wrong contact holes observed in one field of view calculation was measured as the wrong contact hole. The smaller the number of the wrong contact holes, the better the result. 0 From the evaluation results of Table 4, it can be understood that the composition of the photoresist pattern forming method of the present invention is excellent in sensitivity, and the photoresist according to the composition of the present invention is used. According to the pattern forming method, it is understood that a hole pattern having a good shape in which a wrong contact hole does not occur can be formed. [Industrial Applicability] The present invention can provide a method for forming a photoresist pattern which is excellent in sensitivity and which is difficult to generate a wrong contact hole in the case of using an organic solvent-containing developing solution, that is, excellent in lithography characteristics. And a radiation sensitive resin composition. -67-

Claims (1)

201219972 VII. Patent application scope: 1. A method for forming a photoresist pattern, which comprises a photoresist pattern forming method of the following steps: (1) forming a photoresist film on a substrate by coating a radiation-sensitive resin composition a step of (2) an exposure step, and (3) a step of developing using a developing solution containing 80% by mass or more of an organic solvent, and characterized in that the radiation-sensitive resin composition contains: [A] having an acid a dissociative group-based base polymer, [B] a cation having a cation and an anion having an alicyclic group, and having an atomic ratio (F/C) of a fluorine atom to a carbon atom of the anion of 0.1 or more and 0.5 or less The acid generator, and [C] a polymer containing a fluorine atom and having a fluorine atom content higher than that of the [A] polymer. 2. The method for forming a photoresist pattern according to claim 1, wherein the acid dissociable group of the [A] polymer has a monocyclic or polycyclic alicyclic hydrocarbon group. 3. The method for forming a photoresist pattern according to claim 1, wherein the anion of the [B] radiation-sensitive acid generator is represented by the following formula (1): [Chemical Formula 1] / Rf1 -68- 201219972 (In the formula (1), R1 is a monovalent organic group having a monocyclic or polycyclic alicyclic group, η is 1 or 2, and Rfl and Rf2 are each independently a hydrogen atom, a fluorine atom or a carbon number. The fluorinated alkyl group 'except when Rfl&amp;Rn is a hydrogen atom, and when 11|'1 and 1^2 are each plural', the plural RfI and Rf2 may be the same or different) 〇4. The method for forming a photoresist pattern according to the first aspect, wherein the anion having an alicyclic group of the [B] radiation-sensitive acid generator is a group composed of anions represented by the following formulas (2) to (5), respectively. At least one anion selected by the group 'Chemical 2】 [Chemical 3] F2 _ C, p, S03 92 (7) [Chemical 4] F2, C, SO·, c/S〇3- F2 (3) (4) -69- 201219972 【化5】 F2 /C\ c S〇3~ (5) 卜2 o 5 . The method for forming a photoresist pattern according to claim 1, wherein the organic solvent is an alcohol solvent, an ether solvent, a ketone solvent, At least one solvent selected from the group consisting of a guanamine solvent, an ester solvent, and a hydrocarbon solvent. 6. A radiation sensitive resin composition which is a radiation sensitive resin composition for organic solvent development and which comprises: [A] a base polymer having an acid dissociable group, [B] containing a cation-sensitive acid generator having a cation and an anion having an alicyclic group, and having an atomic ratio (F/C) of a fluorine atom to a carbon atom of the anion of 0.1 or more and 0.5 or less, and [C] containing fluorine A polymer having an atomic and fluorine atom content higher than that of the [A] polymer. -70- 201219972 Four designated representatives: (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: No 201219972 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention: no