TW201211688A - Pattern-forming method and radiation-sensitive resin composition - Google Patents

Abstract

The present invention is a trench pattern-forming or hole pattern-forming method comprising (1) a step for forming a resist film in which a radiation-sensitive resin composition is applied to a substrate, (2) an exposure step in which radiation is irradiated onto the resist film via a photomask, and (3) a development step in which the exposed resist film is developed, wherein the trench pattern-forming or hole pattern-forming method is characterized in that the radiation-sensitive resin composition comprises: [A] a polymer containing 10 mol% or less of structural units having acid-dissociating groups; [B] a polymer containing more than 10 mol% of structural units having acid-dissociating groups; and [C] a radiation-sensitive acid generator, and the development solution for the development step (3) comprises 80 mass% or more of an organic solvent.

Description

201211688 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a pattern forming method and a radiation sensitive linear resin composition. [Prior Art] As the structure of various electronic devices such as semiconductor devices and liquid crystal displays is miniaturized, the pattern of the resist pattern in the lithography step is required to be miniaturized. At present, for example, an ArF excimer laser can be used to form a fine resist pattern having a line width of about 90 nm, but in the future, a finer pattern is required. On the other hand, even if a light source of the same exposure wavelength is used depending on the immersion exposure, 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 caused by substances in the uranium-proofing agent. The dissolution of the immersion medium deteriorates the resist film, and the performance thereof is degraded. The eluted material locally changes the refractive index of the liquid immersion medium, and the dissolved material contaminates the surface of the resist, thereby adversely affecting the characteristics of the lithography. Defects (refer to the International Publication No. 04/068242). With regard to this defect, it is considered to increase the hydrophobicity of the resist film, and for this reason, it is necessary to change the resist composition. These changes tend to deteriorate the lithographic characteristics. In addition, 'Technology for improving the resolution using the characteristics of chemically amplified uranium-resistant materials' is known as a double exposure technique and a dual patterning technique, but the technique of improving the image of the solution is improved without increasing the steps of using the existing device. A technique of using an organic solvent having a polarity lower than that of an alkaline aqueous solution in a developing solution is disclosed (refer to Japanese Laid-Open Patent Publication No. 2000-99953). When the image forming liquid is formed into a groove pattern or a hole pattern using an alkaline aqueous solution, it is difficult to form a fine pattern due to lack of optical contrast, but when an organic solvent is used, optical contrast can be improved, so that it can be formed. Fine pattern. With regard to the use of the resist pattern as described above for immersion exposure, especially in the formation of a groove pattern or a hole pattern, the most suitable sensitive radiation linear resin composition, the used developing liquid, and the like have not been found so far. A combination of the same. [PRIOR ART DOCUMENT] [Patent Document 1] [Publication Document 1] International Publication No. 04/068242 (Patent Document 2) JP-A-2000-119953 The object of the above problems is to provide a method for forming a groove pattern or a hole pattern excellent in lithography characteristics, and a radiation sensitive linear resin composition. [Means for Solving the Problem] The invention for solving the above problems is: a method for forming a groove pattern or a hole pattern, which comprises a method of forming a groove pattern or a hole pattern of the following steps: (1) sensitizing radiation a step of coating a linear resin composition on a substrate to form an anti--6-201211688 etching film, (2) exposing the resist film to radiation through a photomask, and (3) causing the exposed resist film The imaging step of developing, characterized in that the sensitive radiation linear resin composition contains: [A] a polymer having a structural unit of an acid dissociable group in a proportion of 10 mol% or less (hereinafter also referred to as "[A Polymer]), [B] a polymer having a structural unit of an acid dissociable group in an amount exceeding 10 mol% (hereinafter also referred to as "[B] polymer"), and [C] linearity of sensitivity radiation The acid generator, and the developing solution in the above (3) development step contains 80% by mass or more of an organic solvent. [A] The polymer has a structural unit having an acid dissociable group of 10 mol% or less, and since the dissociation of all the acid dissociable groups does not impair the solubility of the [A] polymer to the developing solution, Defects such as residue or bleed out are suppressed. Here, the structural unit having an acid dissociable group means a structural unit in which a hydrogen atom of a polar group such as a carboxyl group is substituted with an acid dissociable group. In another aspect, the [B] polymer has more than 10 mol% of a structural unit having an acid dissociable group, and the acid dissociable group functions by an acid generated from the linear acid generator of the [C] sensitive radiation. Dissociation. As a result, the polarity is increased, the poor solubility of the [B] polymer in the exposed portion is increased, and the dissolution of the polymer in the resist film in the unexposed portion to the developing liquid is promoted. Further, in the pattern forming method, an organic 201211688 solvent imaging solution having a lower polarity than the alkaline aqueous solution used for the formation of the positive-type chemical amplification resist as a developing liquid in the developing step is used (dissolvable) The unexposed portion of the resist film forms a developing solution of a negative image, and the organic solvent is excellent in affinity with the surface of the resist film, and as a result, the developability is improved. According to this, by combining the pattern forming methods of the specific compositions and features, it is possible to form a pattern having excellent lithographic properties such as sensitivity, cross-sectional shape, circularity of the hole pattern, and resolution. [A] The fluorine content of the polymer is preferably higher than that of the [B] polymer. When the fluorine content of the polymer [A] is higher than that of the [B] polymer, the polymer [A] tends to be partially localized in the vicinity of the surface of the resist film, and the acid generator or the liquid during the immersion exposure can be suppressed. The acid diffusion controlling agent or the like is dissolved in the liquid immersion medium. Further, the contact angle of the resist film and the liquid immersion medium can be controlled within a desired range, and the occurrence of bubble defects can be suppressed. Further, it is possible to increase the back contact angle of the resist film and the liquid immersion medium, and to perform scanning exposure at a high speed without leaving water droplets remaining. The organic solvent contained in the developing solution is preferably at least one organic solvent selected from the group consisting of an ether solvent, a ketone solvent, and an ester solvent. By using the above specific organic solvent, an appropriate combination with a specific resist composition can be achieved, and a pattern excellent in lithographic characteristics can be obtained. The polymer [A] preferably has at least one structural unit selected from the group consisting of the structural unit (I) represented by the following formula (1) and the structural unit (II) represented by the following formula (2), -8 - 201211688 【化1】

Ο (1) (In the formula (1), R1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and R2 is a linear or branched alkyl group having a carbon number of 1 to 6 or a carbon number of 4 to 2. a one-valent alicyclic hydrocarbon group, but at least a part of the hydrogen atom of the above alkyl group and the alicyclic hydrocarbon group is substituted by a fluorine atom), [Chemical 2]

(In the formula (2), R3 is a hydrogen atom, a methyl group or a trifluoromethyl group, R4 is a (m+1)-valent linking group, X is a divalent linking group having a fluorine atom, and R5 is a hydrogen atom or a monovalent group. The organic group, m is an integer from 1 to 3, but when m is a complex number, the plurality of X and R5 may be the same or different). By having the above-mentioned specific structural unit of the polymer [A], the hydrophobicity of the resist film having a fluorinated group in the structure can be improved, and the substance elution suppression at the time of liquid immersion exposure is excellent. In addition, the retreat contact angle of the resist film and the liquid immersion liquid can be made sufficiently high, and the effect of -9-201211688 can be exhibited when the high-speed scanning exposure is performed, and the usefulness for immersion exposure is high. The acid-dissociable group of the [B] polymer preferably has a chain hydrocarbon group or a monocyclic or polycyclic alicyclic hydrocarbon group. [B] Since the acid-dissociable group of the polymer has the above specific group, the transparency of the resist film to the ArF excimer laser or the like can be improved, and a pattern having more excellent resolution can be formed. The sensitive radiation linear resin composition of the present invention is a method for forming a groove pattern or a hole pattern including the following steps: (1) a step of applying a radiation sensitive linear resin composition on a substrate to form a resist film, (2) a step of exposing the resist film to radiation by a mask, and (3) a step of developing the exposed resist film, wherein the developing solution in the step (3) contains 80% by mass or more An organic solvent characterized by comprising: [A] a polymer having a structural unit of an acid dissociable group in a proportion of 10 mol% or less, [B] a structure having an acid dissociable group; A polymer containing more than 10 mol% of the unit, and a linear acid generator of [C] sensitive radiation. [Effect of the Invention] The present invention can provide a groove pattern or a hole pattern which is suitable for liquid immersion exposure and which is excellent in lithographic characteristics such as sensitivity and cross-sectional shape, such as circularity and resolution. And a sensitive radiation linear resin composition. [Embodiment] <Form Forming Method> The pattern forming method of the present invention comprises the following steps: (1) a resist film forming step of applying a radiation sensitive linear resin composition onto a substrate, and (2) a transmissive mask pair The exposure step of the resist film irradiating the radiation, and (3) the step of developing the exposed resist film. Each step is detailed below. [Step (1)] This step is a step of applying the radiation sensitive linear resin composition of the present invention onto a substrate to form a resist underlayer film. As the substrate, a conventionally known substrate such as a twinned wafer or an aluminum-coated wafer can be used. Further, an organic or inorganic antireflection film may be formed on the substrate. The coating method is exemplified by spin coating, casting coating, roll coating, and the like. Further, the film thickness of the resist film to be formed is usually Ο.ΟΙμπι~Ιμιη, preferably 0·01μηι~0·5μιη. After coating the composition of the sensitive radiation linearly, the solvent in the coating film may be volatilized by pre-baking as needed. The heating condition of the crucible is suitably selected according to the composition of the radiation sensitive resin composition, but it is usually from 30 ° C to 200 t, preferably from 50 ° C to 150 ° C. 201211688 A protective film such as, for example, JP-A-5-8 8 5 98 is provided on the resist layer to prevent alkaline impurities and the like contained in the environmental atmosphere. Further, in order to prevent an acid generator or the like from being provided on the resist layer, for example, a protective film for liquid immersion of JP-A-200 5-352384 can be provided. Again, these techniques can be employed. [Step (2)] This step is a step of irradiating the radiation formed in the step (1) through the reticle. Further, exposure can be performed by projection of the liquid as needed. For example, it is possible to reduce the projection exposure by the desired high-line pattern mask, and to form an equal groove exposure, and to perform two or more exposures using the desired pattern and the mask pattern, preferably continuously. exposure. For example, the projected exposure is reduced by the line and interval pattern mask on the desired area, and then the second reduction projection exposure is performed for the exposure of the first exposure. The first two exposure portions are preferably orthogonal. The liquid immersion liquid which can be easily used to form a circular contact hole pattern light in the surrounding unexposed portion by orthogonality is exemplified as water or a fluorine-based inert liquid, and the exposure wavelength is transparent, and in order to be projected on the film The upper optics are kept to a minimum, so the temperature coefficient of the refractive index is better, but especially when the exposure light source is ArF excimer laser light (bubble, in addition to the above viewpoint, it is easy to obtain, easy to operate, and easy to use water. When water is used, a slight reduction effect may be added, and the outflow of the disclosed protective liquid may be reported, and the above-mentioned resist immersion liquid may be disclosed to reduce the transmission pattern in the domain. , the first part of the line, so that the line exposure part and the first exposure part. In addition, exposure. Liquid immersion liquid object deformation may be small liquid: length 1 9 3 nm), in terms of water Surface Zhang-12- 201211688 The additive that simultaneously increases the interfacial activity. Preferably, the additive does not dissolve the resist layer on the crystal, and the effect on the optical coating under the resist is negligible. The water used is preferably distilled water. The radiation used in the exposure is suitably selected depending on the type of the [C] sensitive radiation linear acid generator, and is exemplified by ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like. In these, the exposure conditions such as ArF excimer laser light or KrF excimer laser light (wavelength 248 nm), preferably ArF excimer laser light exposure amount, etc. are preferably linear according to the sensitivity radiation. The compounding composition of the resin composition or the kind of the additive is suitably selected. In the pattern forming method of the present invention, the plurality of exposures having the plurality of exposure steps may use the same light source, or 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 P E B, the dissociation reaction of the acid dissociable group in the linear radiation resin composition can be smoothly carried out. The heating condition of P E B is usually from 30 ° C to 2 0 0 ° C, preferably from 50 ° C to 170 ° C. [Step (3)] This step is a step of developing the exposed resist film. Contains organic solvents after exposure. The developing solution used for the development is a method of selectively dissolving and removing the low-exposure portion and the unexposed portion, and is not particularly limited as long as it contains 80% by mass or more of the organic solvent. The organic solvent is, for example, at least one selected from the group consisting of an alcohol solvent, an ether solvent, a ketone organic solvent, a guanamine organic solution, an ester organic solvent, and a hydrocarbon organic solvent. -13- 201211688 Alcohol solvents are listed, for example: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, n-pentanol, isoamyl alcohol ' 2 -methylbutanol' second pentanol, third pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, second hexanol, 2-ethylbutanol, first heptanol , 3 -heptanol, n-octanol, 2·ethylhexanol, second octanol, n-nonanol 2,6-dimethyl-4-heptanol, n-nonanol, second-undecyl alcohol , trimethyl sterol, second-dodecanol, second-b hospital alcohol, sugar alcohol, hydrazine, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, a monoalcoholic solvent such as benzyl alcohol or diacetone alcohol; ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4·pentanediol, 2-methyl-2,4-pentyl Multivalents such as diol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1&gt;3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, etc. Alcohol solvent; 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, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, two Ethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl The oxime ether solvent such as a polyvalent alcohol partial ether solvent such as ether is exemplified by diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, methoxybenzene or the like. The ketone solvent is exemplified by, for example, acetone, methyl ethyl ketone, methyl n-propyl-14-201211688 ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone. , ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl fluorenone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2, A ketone solvent such as 4-pentanedione, etidylacetone or acetophenone. The guanamine solvent is exemplified by, for example, N,N'-dimethylimidazolidinone, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, B. Indoleamine, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, and the like. The ester solvent is exemplified by, for example, diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, Isobutyl acetate, second butyl acetate, n-amyl acetate, second amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethyl acetate Hexyl ester, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-decyl acetate, methyl acetoxyacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, acetic acid Glycol monoethyl 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 monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, acetic acid Oxyl tri-diol ester, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, oxalic acid Esters, methyl lactate, ethyl lactate, n-butyl acrylate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl terephthalic acid. -15- 201211688 Hydrocarbon solvents are listed, for example: Zhengwuyuan, Yiwuyuan, Zhengjiyuan, Yijiyuan, Zhenggengyuan, Yigengyuan, 2,2,4-trimethylpentane, n-octane, and An aliphatic hydrocarbon solvent such as octane, cyclohexane or methylcyclohexane; benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, An aromatic hydrocarbon solvent such as isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene or n-pentylnaphthalene; and the organic solvent is preferably an ether system. At least one organic solvent selected from the group consisting of a solvent, a ketone solvent and an ester solvent, more preferably n-butyl acetate 'isopropyl acetate, amyl acetate, methyl ethyl ketone, methyl n-butyl ketone, Methyl n-amyl ketone, anisole. By using the above specific organic solvent, an appropriate combination with a specific resist composition can be achieved, and a pattern excellent in lithographic characteristics can be obtained. Further, these organic solvents may be used singly or in combination of two or more. The developer may be added with an appropriate amount of surfactant as needed. The surfactant is exemplified by an ionic or nonionic fluorine-based surfactant, a lanthanoid surfactant, and the like. 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. -16- 201211688 In the formation of this pattern, it is preferred to wash the anti-uranium film with a washing liquid after the development of the step (3). Further, the washing liquid in the washing step can also be used to effectively wash the generated dross using an organic solvent _ '. The washing liquid is preferably a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent or the like. Among these, an alcohol-based solvent 'ester-based solvent is preferred, and more preferably a carbon number of 6 to 8 one-valent alcohol-based solvent. The one-valent alcohol having 6 to 8 carbon atoms is exemplified by a linear, branched or cyclic valence 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-octyl alcohol, benzyl alcohol, and the like. Among these, 1-hexanol, 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. Good visibility can be obtained by setting the water content to 1% by mass or less. Further, an interface active agent 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 onto a substrate 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. <Thermal radiation linear resin composition> The radiation sensitive linear resin composition used in the present invention contains the [A] polymer, the [B] polymer, and the [C] radiation sensitive linear acid generator. [A] The polymer contains a structural unit having an acid dissociable group of 1 〇 mol% or less -17-201211688, and does not impair the dissociation of all the acid dissociable groups. [A] Polymer pair imaging solution Since it has solubility, it can suppress the occurrence of defects such as residue or bleeding. Here, the structural unit having an acid dissociable group means a structural unit in which a hydrogen atom of a polar group such as a carboxyl group is substituted with an acid dissociable group. On the other hand, the [B] polymer has more than 10 mol% of a structural unit having an acid dissociable group, and the acid dissociable group is acted upon by an acid generated by the [C] sensitive radiation linear acid generator. Dissociation. As a result, the polarity is increased, and the poor solubility of the polymer [B] in the exposed portion is increased, and the dissolution of the polymer in the resist film in the unexposed portion with respect to the developing liquid is promoted. Further, the radiation sensitive linear resin composition may contain an optional component as long as it does not impair the effects of the present invention. The ingredients are detailed below. <[A] Polymer> [A] The polymer is a polymer having a structural unit of an acid dissociable group and having a ratio of 10 mol% or less. By setting the content of the acid-dissociable group to 10% by mole or less, even if the entire dissociable group dissociates without impairing the solubility in the developing solution, the residue or the residue can be suppressed. Defects such as oozing occur. The structural unit having an acid dissociable group is exemplified by a structural unit (III) represented by the formula (5) described later. The content ratio of the structural unit having an acid dissociable group in the polymer [A] is preferably 〇 mol%. Further, the [A] polymer preferably has a higher fluorine content than the [B] polymer. When the fluorine content of the polymer [A] is higher than that of the [B] polymer, the [A] polymer tends to be locally biased near the surface of the resist film, and the acid generator or the acid anhydride which is exposed to liquid immersion can be suppressed. The diffusion controlling agent or the like is dissolved in the liquid immersion medium. -18 - 201211688 In addition, the contact angle of the resist film and the liquid immersion medium can be controlled within a desired range, and the occurrence of bubble defects can be suppressed. In addition, the back contact angle of the resist film and the liquid immersion medium can be increased, and the exposure can be performed at a high speed without leaving water droplets. 0. The state of the polymer [A] containing a fluorine atom is exemplified as (i) the fluorine bond in the main chain. The structure of the alkyl group, the structure of the fluorinated alkyl group bonded to the (U) side chain, the structure of the (iU) main chain and the fluorinated alkyl group bonded to the side chain, etc., and the polymer having the structure of (i) is obtained. The monomers are exemplified by, for example, an α-trifluoromethyl acrylate compound, a β-trifluoromethyl acrylate compound, an α,β-trifluoromethyl acrylate compound, and hydrogen of one or more vinyl sites via a trifluoromethyl group. Alkyl substituted compounds and the like. The monomer obtained by obtaining the polymer having the structure of (ii) is exemplified by a fluorinated alkyl group of an alicyclic olefin compound such as norbornene, a fluorinated alkyl ester of acrylic acid or methacrylic acid, or more. The side chain of the olefin (the portion containing no double bond) is a fluorinated alkyl group or a derivative thereof. The monomer which obtains the polymer having the structure of (iii) is exemplified by, for example, α-trifluoromethyl acrylate, acrylic acid (3-trifluoromethyl ester, α-β-trifluoromethyl acrylate, etc., a side chain of a fluorinated alkyl group. An ester compound of a derivative thereof, or a side chain of a compound obtained by substituting a hydrogen atom of one or more vinyl sites with a fluorinated alkyl group such as a trifluoromethyl group, substituted by a fluorinated alkyl group or a derivative thereof, and bonded The hydrogen on the double bond of one or more kinds of alicyclic hydrocarbon compounds is substituted by a fluorinated alkyl group such as a trifluoromethyl group, and the side chain is a fluorinated alkyl group or a derivative thereof, etc. Further, an alicyclic hydrocarbon The compound represents a compound in which a part of the ring is a double bond. The [Α] polymer preferably has a structural single group represented by the structure represented by the above formula (1), the single--19-201211688 (I) and the above formula (2). At least one structural unit is selected. In addition, [the structural unit (I) and the structural unit (II) are included.] [A] The polymer may have two or more structural units. [Structural unit (I)] The structural unit (I) is represented by the above formula (1) in the formula (1) where 'R1 is a hydrogen atom The gas atom and R2 are a linear or branched alkyl group or an indole ring hydrocarbon group described above. However, at least a part of the above alkyl group and the alicyclic hydrocarbon group are substituted by a fluorine atom. The carbon number represented by the above R2 is 1 to 6 The linear form is, for example, a methyl group, an ethyl group, a n-propyl group, a n-butyl group or the like, and a carbon number of 4 to 20, represented by the above R 2 , such as a cyclopentyl group, a cyclopentylpropyl group, a cyclohexyl group, or a ring. Hexacyclooctyl, cyclooctylmethyl, etc. As for the structural unit (I), it is preferably a structural unit which is not represented by the following formula. The group of the group (II) is a] the polymer may also have "other structural units" Structural unit. The structural unit shown below. Upper methyl or trifluoromethyl group Carbon number 4 to 20 One-valent ester has a hydrogen atom or a branched alkyl group, and an anthracene-type hydrocarbon group is exemplified as an example methyl group. 'Cycloheptyl, (1-1), ( 1-2) • 20- 201211688 【化3】 R1

F3c above (1-

Obtained the structure of trifluoromethyl monoester, (perfluoroethyl acrylate, perfluoroisopropyl acrylate) perfluoroisomethyl acrylate 1,1,1,3,3,3-hexa; 2.2.3.3.4.4.5.5 - 2.2.3.3.4.4.5.5- , methyl ester, (meth) acrylic acid 1 - ( 2, 1- ( 3,3,4,4,5,5, (meth) acrylate, etc. [A] Polymerization of one structural unit. The monomer of the preferred position (I) is exemplified by, for example, (meth)acrylomethyl)acrylic acid 2,2,2-trifluoroethyl ester, (methyl), (meth)acrylic acid perfluoro-positive Propyl ester, (meth) ester, perfluoro-n-butyl (meth)acrylate, (methyl butyl ester, perfluorotributyl (meth) acrylate) (perfluorocyclohexyl ester, (meth)acrylic acid 2-(murine)propyl ester, 1-(octafluoro)pentyl (meth)acrylate, 1-(/fluorene)hexyl (meth)acrylate, 1-fluoro(cyclo)acrylic acid (per) 2,2,3,3,3-pentafluoro)propyl ester, (methyl 2,3,3,4,4,4-heptafluoro)pentyl ester, (meth)acrylic acid 6'6'7'7' 8'8'9'9'1〇,1〇,1〇_heptadecafluoro)decyl ester, 1-(5-trifluoromethyl_3,34,4,5,6,6,6 octafluoro) Structure sheet in the kiss (1) The content ratio is all in the range of 3 〇 mol% to 100 mol%. -21 - 201211688 [Structural unit (II)] The structural unit (II) is a structural unit represented by the above formula (2), In the formula (2), R3 is a hydrogen atom, a methyl group or a trifluoromethyl group, and R4 is a (m+1)-valent linking group. X is a divalent linking group having a fluorine atom. R5 is a hydrogen atom or a monovalent organic group. The m is an integer of 1 to 3. However, when m is a complex number, the plurality of X and R5 may be the same or different. The linking group of the (m+Ι) valence represented by the above R4 is, for example, a carbon number of 1~. a linear or branched hydrocarbon group of 30, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a combination of the group and an oxygen atom, a sulfur atom or an ether group a group in which one or more groups selected from the group consisting of an ester group, a carbonyl group, an imido group, and a guanamine group are added. The (m+Ι)-valent linking group may have a substituent. The linear or branched hydrocarbon group of 1 to 30 is exemplified by, for example, methane, ethane, propane, butane, pentane, hexane 'heptane, decane, eicosane, and tridecane. The hydrocarbon group is obtained by removing (m + Ι) a hydrogen atom, etc. The alicyclic hydrocarbon group having 3 to 30 carbon atoms is exemplified by, for example, removing (m + Ι) hydrogen atoms from the following hydrocarbons: Monocyclic saturated hydrocarbons such as propane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, methylcyclohexane, ethylcyclohexane; cyclobutene, cyclopentane a monocyclic unsaturated hydrocarbon such as a olefin, a cyclohexene, a cycloheptene, a cyclooctene, a cyclodecene, a cyclopentadiene, a cyclohexadiene, a cyclooctadiene or a cycloolefin; -22- 201211688 [2.2.1] Heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.02, 6] decane, tricyclo[3.3.1.1'7] decane, tetracyclo[6.2.1.13'6.02' 7] Polycyclic saturated hydrocarbons such as dodecane and adamantane: Bicyclo[2.2.1]heptene, bicyclo[2.2.2]octene, tricyclo[5.2.1.02'6].decene, tricyclo[ 3.3.1.13 '7] Polycyclic hydrocarbon groups such as terpene and tetracyclo[6.2.1.13'6.02'7] dodecene. The aromatic hydrocarbon group having 6 to 30 carbon atoms is exemplified by, for example, benzene, naphthalene, phenanthrene, anthracene, tetracene (pentacene), pentaacene, pentane, picene, toluene, xylene, An aromatic hydrocarbon such as ethylbenzene, mesitylene or cumene is formed by removing (m+1) hydrogen atoms. The substituent of the above (m+Ι) valence may have a substituent such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, An alkyl group such as a third butyl group or a cyclohexyl group, a hydroxyl group, a cyano group, a hydroxyalkyl group having 1 to 1 carbon number, a carboxyl group, a carbonyl group or the like. The divalent linking group having a fluorine atom represented by the above X is exemplified by a divalent linear hydrocarbon group having 1 to 20 carbon atoms and having a fluorine atom. The divalent linear hydrocarbon group having 1 to 20 carbon atoms having a fluorine atom is, for example, a group represented by the following formulas (X-1) to (X-6). [Chemical 4] cf3 FIFIFIFI CF3 cf3 I 3 1 IIIIII | IIIII —c— I 1 cf3 IFIFIFIHIHIF (X-1) (X-2) (X-3) (X-4) (X-5) (X-6 And X is preferably a group represented by the above formula (X-1) or formula (X-2), and the one group of the organic group is represented by a linear group of, for example, a carbon number of 1 to 30. Or a branched hydrocarbon group, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a combination of the same and an oxygen atom, a sulfur atom, an ether group, an ester group, a carbonyl group or an imine group A group formed by one or more groups selected from the group consisting of a group and a guanamine group. The group represented by the above R5 is preferably a hydrogen atom from the viewpoint of improving the solubility of the polymer in the developing solution. The structural unit (II) is exemplified by a structural unit represented by the following formula (2-1) and formula (2-2). 【化5】

(2-2) In the above formula (2-1), R4 is a divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. R3, X and R5 are synonymous with the above formula (2). In the above formula (2-2), R3, X, R5 and m are the same as the above formula (2). However, when m is a complex number, a plurality of X and R5 may be the same or different. As for the structural unit (II), it is preferably a structural unit represented by the following formula -24- 201211688 [Chem. 6]

In the above formula, the 'r3 system is synonymous with the above formula (2). The monomer which obtains the structural unit (II) is exemplified by (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-3-propyl) (meth)acrylic acid, (meth)acrylic acid Trifluoro-2-trifluoromethyl-2-hydroxy-4-butyl), (meth)acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-5-pentyl) Ester), (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-pentyl) (meth)acrylate, 2-{[5-(1) ',1,1,-Trifluoro-2,-trifluoromethyl-2'-hydroxy)propyl]bicyclo[2.2"]heptyl}ester. [A] The content of the structural unit (Π) in the polymer is preferably 30 mol per 100 mol% of the total structural unit ^ [other structural units] [A] the polymer may further have a control As a structural unit having a lactone structure, a structural unit having a cyclic carbonate structure, and an alicyclic structure-structured lipid structure sheet - 25-201211688 for improving the etching resistance, etc. "." The structural unit having a lactone structure and the structural unit having a cyclic carbonate structure are exemplified by a structural unit represented by the following formula. Here, the base having a lactone structure means a ring group containing a ring (lactone ring) containing a -〇-c(〇)-structure, and the lactone ring is calculated as a ring-only lactone ring. The case is called a monocyclic group, and when it has other ring structures, it is called a polycyclic group regardless of its structure. 【化7】

-26- 201211688

【化8】

In the above formula, the ruler is a hydrogen atom, a methyl group or a trifluoromethyl group. The monomer having a structural unit having a lactone structure is exemplified by a compound represented by the following formula (L-1). The monomer having the structural unit having the above-described lactone structure is preferably a monomer described in the specification of International Publication No. 2 007/1 16664. The structural unit having an alicyclic structure is listed, for example, by the following formula (4). Construction units, etc. [Chemical 9] R6

-27- (4) 201211688 In the above formula (4), R6 is a hydrogen atom, a methyl group or a trifluoromethyl group. X2 is an alicyclic hydrocarbon group having 4 to 20 carbon atoms. Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms are, for example, cyclobutane, cyclopentane, cyclohexane, bicyclo[2.2,1]heptane, bicyclo[2.2.2]octane, and tricyclo[5.2.1.02'. 6] decane, tetracyclo[6·2·1.13'6.02'7]dodecane, tricyclo[3.3.1.I3'7]decane, and the like. These alicyclic hydrocarbon groups having 4 to 20 carbon atoms may have a substituent. As the substituent, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, a t-butyl group, or the like has a carbon number of 1 to 4 A chain, a branched or cyclic alkyl group, a hydroxyl group, a cyano group, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group, an oxygen atom or the like. The monomer which obtains the structural unit containing an alicyclic compound is exemplified by, for example, (meth)acrylic acid-bicyclo[2.2.1]hept-2-yl ester, (meth)acrylic acid-bicyclo[2.2.2]oct-2- Base ester, (meth)acrylic acid-tricyclo[5.2.1.02'6]癸-7-yl ester '(meth)acrylic acid-tricyclo[3.3.1.13'7]indol-1-yl ester, (methyl Acrylic acid-tricyclo[3.3.1.I3'7]non-2-yl ester and the like. Further, the [Α] polymer preferably does not have a structural unit containing an aromatic group. In particular, when an ArF light source is used, there is a case where the sensitivity is lowered. [[A] Polymer synthesis method] [A] The polymer can be made to correspond to a specific structural unit by, for example, using a radical polymerization initiator. The monomer is polymerized in a suitable solvent to produce -28-201211688. The solvent used in the above polymerization is exemplified by the following: alkane such as n-pentane, n-hexane, n-heptane, n-octane, n-decane or n-decane; Alkane such as cyclohexane, cycloheptane, cyclooctane, decahydronaphthalene or norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; chlorobutane and bromine Halogenated hydrocarbons such as hexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate; , ketones such as 2-butanone, 4-methyl-2-pentanone, and 2-heptanone; ethers such as tetrahydrofuran, dimethoxyethane, and diethoxyethane » Methanol, ethanol, 1 An alcohol such as propanol, 2-propanol or 4-methyl-2-pentanol. These solvents may be used singly or in combination of two or more. The reaction temperature in the above polymerization is usually from 40 ° C to 150 ° C, preferably from 50 ° C to 120 ° C. The reaction time is usually from 1 hour to 48 hours, preferably from 1 hour to 24 hours. [A] The weight average molecular weight of the polymer measured by gel permeation chromatography (GPC) in terms of polystyrene (Mw) ) preferably from 1,000 to 50,000 &gt; more preferably from 1,000 to 30,000, most preferably from 1, 〇〇〇 to 10,000. [A] When the Mw of the polymer is less than 1, the sufficient contact angle is not obtained. On the other hand, when Mw exceeds 50,000, the developability as an anti-uranium agent tends to decrease. -29- 201211688 [A] The ratio of the Mw of the polymer to the number average molecular weight (?η) in terms of polystyrene by the GPC method is usually from 1 to 3, preferably from 1 to 2. In addition, Mw and Μη in this specification use GPC column (2 TOSOH company 'G2000HXL, 1 G3000HXL, 1 G4000ΗXL), and the following conditions are determined.

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μΙ&gt; Detector: Differential refractometer standard substance: Single The dispersed polystyrene <[Β] polymer> [Β] polymer is a polymer having a structural unit having an acid dissociable group and having a content of more than 10 mol%. Further, the [Β] polymer is a polymer which is increased in polarity by an action of an acid and which is insoluble or insoluble to a developing liquid containing an organic solvent. [Structural unit (III)] The structural unit having an acid dissociable group is, for example, a structural unit (III) represented by the following formula (5). -30- 201211688

In the above formula (5), R7 is a hydrogen atom, a methyl group or a trifluoromethyl group, and RP is an acid dissociable group. The above acid-dissociable group represented by Rp is preferably a group represented by the following formula. [Chemical Formula 1] RP1 - C - Rp3 (6) In the above formula (6), Rpl is an alkyl group having a carbon number or a alicyclic hydrocarbon group having a carbon number of 4 to 2 Å. Rp2 and Rp3 are each independently an alkyl group having a carbon number of ～4 or an alicyclic hydrocarbon group having a carbon number of 4 to 20. Further, Rp2 and Rp3 may be bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms together with each of the bonded carbon atoms. However, part or all of one of the hydrogen atoms of the groups may be substituted by a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. The above alkyl group having 1 to 4 carbon atoms represented by Rpl, 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 carbon number 4 to 20 one-valent alicyclic hydrocarbon group represented by Rpl, Rp2 and Rp3 is exemplified by, for example: -31 - 201211688 Polycyclic alicyclic group having an adamantane structure and a norbornane structure; cyclopentane, A monocyclic alicyclic group having a naphthene structure such as cyclohexane. Preferably, the acid dissociable group represented by Rp is 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 structure or a naphthene structure. The structural unit (III) is exemplified by a structural unit represented by the following formula, and the like. [1 2]

-32- 201211688

-33- 201211688 In the above formula, R is synonymous with the above formula (5). The content ratio of the structural unit (111) in the [B] polymer is preferably from 20 mol% to 60 mol% based on the total structural unit. Further, the [b] polymer may have one or two or more structural units (ΠΙ). [Structural unit (IV)] The polymer [B] preferably has a structural unit (IV) derived from an acrylate having no fluorine atom and having a lactone structure. By making the [B] polymer have a structural unit (IV), the adhesion of the resist film to the substrate can be improved. As the structural unit (IV), a structural unit having no fluorine atom as the structural unit having the lactone structure as the "other structural unit" described above can be used. The content ratio of the structural unit (IV) in the [B] polymer is preferably from 30 mol% to 60 mol% based on the entire structural unit. [Other structural units] [B] Polymers may also have a single structure in terms of structural units (ΠΙ) and structural units. He is in his own position. The position of the single table is the same as that of the other. It is the same as the same. It has an IV containing C such as -34- 201211688 [Chemical 1 4]

Ο

ο ο -35- 201211688 【化1 5】

In the above formula, 'R8 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. [B] The content of the structural unit (v) in the polymer is preferably from 〜 mol % to 30 mol % ‘more preferably 〇 mol % to 2 〇 mol %. <B] Method for synthesizing polymer> A radical polymerization initiator is produced by polymerizing a monomer in a unit. [B] The polymer can be specifically used in a solvent corresponding to each structure, for example, by using a suitable solvent. Listed as 1 the same solvent as those listed in the method of polymer synthesis 201211688. The reaction temperature in the polymerization is usually from 4 ° C to 150 ° C', preferably from 50 ° C to 120 ° C. The reaction time is usually from 1 hour to 48 hours, preferably from 2 hours to 24 hours. The molecular weight of the [B] polymer measured by the GPC method is preferably from 1,000 to 1,00,000, more preferably from 1,000 to 50,000, and most preferably from 1,000 to 30,000. When the Mw of the [8] polymer is within the above specific range, it is sufficiently soluble in the resist solvent when used as a resist, and the cross-sectional shape of the dry etching resistant or resist pattern is good. [B] The ratio of Mw to Μη (Mw/Mn) of the polymer is usually from 1 to 3, preferably from 1 to 2. <[C] sensitized radiation linear acid generator> [C] The sensitive radiation linear acid generating system generates an acid by exposure, and the acid dissociates the acid dissociable group present in the [B] polymer to produce an acid. The form of the [C]-sensitive radiation linear acid generator in the linear radiation-sensitive resin composition may be in the form of a compound as described later (hereinafter also referred to as a suitable "C] radiation-sensitive linear acid generator"), or The form which is contained as a structural unit of the [B] polymer or another polymer may be a form in which the two are combined. [C] The sensitive radiation linear acid generator is exemplified by, for example, a gun salt compound, a sulfonimide compound, a halogen-containing compound, a diazoketone compound, and the like. Among the above [C] sensitive radiation linear acid generators, a key salt compound is preferred. The key salt compound is exemplified by, for example, a phosphonium salt (including a tetrahydrothiophene key salt), a phosphonium salt, a scale salt, a diazo salt, a pyridyl salt, and the like. The onium salt is exemplified by, for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium-37-201211688 nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenyl camphorsulfonate, 4-cyclohexylphenyldiphenylphosphonium Fluoromethanesulfonate, 4-cyclohexylphenyldiphenylphosphonium nonafluorobutane sulfonate, 4-cyclohexylphenyldiphenylphosphonium perfluorooctane sulfonate, 4-cyclohexylphenyl Diphenylphosphonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylcamphorsulfonate, 4 - methanesulfonylphenyldiphenylphosphonium trifluoromethanesulfonate, 4-methanesulfonylphenyldiphenylphosphonium nonafluorobutanesulfonate, 4-methanesulfonylphenyl diphenyl锍Perfluoro n-octane sulfonate, 4-methanesulfonylphenyldiphenyl hydrazine 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethane sulfonic acid Salt, 4-methanesulfonylphenyldiphenyl camphorsulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-6-(1-adamantanecarbonyloxy)-hexane-1 - sulfonate and the like. Among these, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluorobutane sulfonate and triphenylsulfonium 1,1,2,2-tetrafluoro-6- (1-golden Alkoxycarbonyl)-hexane-1-sulfonate is preferred. The tetrahydrothiophene key salt is exemplified by, for example, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetra Hydrothienyl hexafluoro-n-butane sulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydropropenyl p-perfluoro-n-octane sulfonate ' 1-(4-n-butoxy) Naphthalen-1-yl)tetrahydrothiophene key 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethane sulfonate, 1-(4-n-butoxynaphthalene) -1-yl) tetrahydrostilbene mothyl sulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophene trifluoromethanesulfonate, 1-(6-n-butoxy Naphthalen-2-yl)tetrahydrothiophene hexafluoro-n-butane sulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophene-perfluoro- n-octane sulfonate, 1-(6 -正-38- 201211688 Butoxynaphthalen-2-yl)tetrahydrothiophene key 2_bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethane sulfonate, 1 -(6-n-butoxynaphthalen-2-yl)tetrahydrothiophene mothyl sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene trifluoromethanesulfonate ', 1-(3,5-Dimethyl-4-hydroxyphenyl)tetrahydrothiophene, nonafluoro-n-butane sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl) Tetrahydrothiophene fluorene perfluoro-n-octane sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene 2-2-cyclo[2·2·1]heptan-2-yl- 1,1,2,2-tetrafluoroethanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene mothyl sulfonate, and the like. Among the tetrahydrothiophene key salts, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene hexafluoro-n-butane sulfonate, 1-(4-n-butoxynaphthalene- 1-yl) tetrahydrothiophene gun perfluoro-n-octane sulfonate and 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene hexafluoro-n-butane sulfonate. The onium salt is exemplified by, for example, diphenyliodotrifluoromethanesulfonate, diphenylsulfonium nonafluorobutanesulfonate, diphenylphosphonium perfluorooctanesulfonate, diphenylphosphonium 2-bicyclopropane. [2.2.1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, diphenyl camphorsulfonate, bis(4-butyltiumphenyl)phosphonium trifluoride Methanesulfonate, bis(4_t-butylphenyl)phosphonium nonafluorobutane sulfonate, bis(4-t-butylphenyl)phosphonium perfluorooctane sulfonate, double (4 _T-butylphenyl) 鎭2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethane sulfonate, bis(4-_t-butylphenyl) Camphor sulfonate and the like. Among these iodide salts, bis(4-t-butylphenyl)phosphonium nonafluoro-n-butanesulfonate is preferred. These [C]-sensitive radiation linear acid generators may be used alone or in combination of two or more. [C] The amount of the sensitive radiation linear acid generator used as the acid generator is ensured as the sensitivity and developability of the resist, and is usually 100 parts by mass of the polymer of -39-201211688 [B]. It is 0.1 part by mass or more and 20 parts by mass or less, preferably 0.5 part by mass or more and 15 parts by mass or less. [C] Sensitive radiation When the amount of the linear acid generator used is less than 0.1 part by mass, the sensitivity and the visibility are low. On the other hand, when the amount of the (C) sensitive radiation linear acid generator is more than 15 parts by mass, transparency is low with respect to the radiation, and it is difficult to obtain a desired resist pattern. <Optional component> The linear composition of the radiation sensitive resin may contain [D] in addition to the [A] polymer, the [B] polymer, and the [C] radiation sensitive linear acid generator, without damaging the effects of the present invention. An acid diffusion controlling agent, an [E] solvent, a surfactant, a compound containing an alicyclic structure, and a sensitizer are optional components. Each of the optional components will be described in detail below. <[Acid Diffusion Control Agent]> [D] The acid diffusion control agent is a diffusion image for controlling the acid generated in the resist coating film from the [C] sensitive radiation linear acid generator by exposure, and suppresses the unexposed region. The effect of the composition of the good chemical reaction, and can improve the storage stability of the obtained linear radiation-sensitive resin composition, and further improve the resolution as the photoresist while suppressing the variation of the standing time from the exposure to the development processing. The linear width of the photoresist pattern changes, and a sensitive radiation linear resin composition excellent in process stability can be obtained. [D] The acid diffusion controlling agent may be in the form of a free compound in the linear composition of the radiation sensitive resin, or may be in the form of a structural unit as a polymer, and may be combined with -40-201211688. Type. [D] The acid diffusion controlling agent is exemplified by, for example, an amine compound, a amide group-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, etc. The amine compound is exemplified by, for example, a mono(cyclo)alkylamine; a di(cyclo)alkyl group; Amines; tri(cyclo)alkylamines; substituted alkylanilines or derivatives thereof; ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylammonium , hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4,-diaminodiphenyl ether 4,4'-diaminobenzophenone, 4,4 '-Diaminodiphenylamine, 2,2-bis(4-aminophenyl)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-dimethylamino) Ethyl)ether, bis(2-diethylaminoethyl)ether, 1-(2-hydroxyethyl)-2-imidazolidinone, 2-mercaptool, N,N,N',N' -肆(2-hydroxypropyl)ethylenediamine, N,N,N, , N,,, N"_pentamethyldiethylenetriamine, etc. As the compound containing a guanamine group, for example, an N-tert-butoxy group-containing amine compound, formamide, N-methylformamidine is exemplified. Amine, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, acetamide, benzamide, pyrrolidone, N- Pyrrolidone, N-ethenyl-indole-adamantanamine, tris(2-hydroxyethyl) isocyanurate, etc. Urea compounds are listed, for example, as urea, methylurea, 1,1-dimethyls, 1 , 3-dimethylurea, 1,1,3'3-tetramethylurea, anthracene, tris-diphenylurea, tri-n-butylsulfide, etc. -41 - 201211688 Nitrogen-containing heterocyclic compounds are listed, for example, Imidazoles: pyridines; piperazines: pyrazine, pyrazole, pyrimidine, quinoline, hydrazine, pyrrolidine, piperidine, piperidine ethanol, 3-piperidinyl-1,2-propanediol, morpholine, 4 -methylmorpholine, 1-(4-morpholinyl)ethanol, 4-ethinylmorpholine, 3-(N-morpholinyl)-1,2-propanediol, 1,4-dimethylpiperazine , 1,4-diazabicyclo[2.2.2]octane, etc. In addition, as for the [D] acid diffusion control agent, it is also possible to use Exposure to light causes a photo-disinfecting base of a weak acid. The photodisintegrat base generates an acid in the exposed portion to improve the insolubility of the [B] polymer to the developing solution, and on the other hand, it acts as an anion in the unexposed portion. The high acid trapping function functions as a quencher and captures the acid diffused from the exposed portion. One example of the photocrackable base is a key salt compound which loses acid diffusion control by exposure decomposition. The key salt compound is listed as For example, an onium salt compound represented by the following formula (7), an onium salt compound represented by the following formula (8), and the like. R18 【化1 6】

(8) In the above formula (7) and formula (8), R18 to R22 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom or -S02-Rc. Rc is an alkane-42-201211688 group, a cycloalkyl group, an alkoxy group or an aryl group. In the above formula (7) and formula (8), Z· is OH·, R23-CO〇-, Rd-S02-N-R23, R23-S03_, or an anion represented by the following formula (9). R23 is a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. However, part or all of the hydrogen atoms of the above alkyl group, cycloalkyl group, aryl group and aralkyl group may also be substituted. RD is a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms. However, part or all of one of the hydrogen atoms of the above alkyl group and cycloalkyl group may be substituted by a fluorine atom. However, when Z· is R23-S03_, there is no case where a fluorine atom is bonded to a carbon atom to which S〇r is bonded. [化1 7]

In the above formula (9), R24 is a linear or branched alkyl group having 1 to 12 carbon atoms or a linear or branched carbon number of 1 to 12 which is partially or wholly substituted by a fluorine atom. Alkoxy. u is an integer of 0 to 2. The above alkyl group represented by R23 is exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group or the like. The above cycloalkyl group represented by R23 is exemplified by, for example, a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tricyclodecyl group, a tetracyclododecyl group, an adamantyl group or the like. The above aryl group represented by R23 is exemplified by a phenyl group, a naphthyl group, an anthracenyl group and the like. -43-201211688 The above aralkyl group represented by R2 3 is exemplified by, for example, a benzyl group, a phenylethyl group, a phenylpropyl group or the like. The substituents which the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group have are exemplified by, for example, a hydroxyl group, a halogen atom, an alkoxy group, a lactone group, an alkylcarbonyl group, and the like. Base, ethyl, propyl, butyl, and the like. The above cycloalkyl group represented by RD is exemplified by, for example, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group or the like. The photocrackable base is exemplified by a compound represented by the following formula.

The [D] acid diffusion controlling agent may be used singly or in combination of two or more. The content of the acid diffusion controlling agent [D] is preferably less than 15 parts by mass based on 100 parts by mass of the [B] polymer. When the content exceeds 15 parts by mass, the sensitivity as a resist tends to decrease. -44 - 201211688 [[E] Solvent] The sensitive radiation linear resin composition usually contains a solvent. The solvent is not particularly limited as long as it can dissolve at least the above-mentioned [A] polymer, [B] polymer, [C] sensitive radiation acid generator, and optional components. The solvent is exemplified by, for example, an alcohol solvent, an ether solvent, a ketone solvent, a guanamine solvent, an ester solvent, and a mixed solvent thereof. Specific examples of the solvent are the same as those exemplified in the above-mentioned pattern forming step (3). Among these, propylene glycol monomethyl ether and cyclohexanone are preferred. These solvents may be used singly or in combination of two or more. [surfactant]

The surfactant has an effect of improving coatability, streaking, and developing properties. As the surfactant, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-decyl phenyl ether, poly Nonionic surfactants such as ethylene glycol dilaurate and polyethylene glycol distearate are also exemplified by the following trade names KP341 (Shin-Etsu Chemical Co., Ltd.), POLYFLOW No. 75, POLYFLOW No. 95 (Kyoeisha Chemical Co., Ltd.), EF TOP EF301, EF TOP EF303, EF TOP EF3 52 (above TOKEMU

PRODUCTS), MEGAFAC F171, MEGAFAC F173 (above is Dainippon Ink Chemical Industry Co., Ltd.), FLORARD FC430, FLORARD FC43 1 (above Sumitomo 3M), ASAHIGUARD AG710, SURFLON S-3 82 'SURFLON SC-101 ' SURFLON - 45- 201211688 SC-102, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-106 (above is Asahi Glass). These surfactants may be used singly or in combination of two or more. [Compound containing an alicyclic structure] A compound containing an alicyclic structure can exert effects such as dry etching resistance, pattern shape, and adhesion to a substrate. [Sensitizer] The sensitizer exhibits an effect of increasing the amount of the [C] sensitive radiation linear acid generator, and exhibits an effect of improving the "apparent sensitivity" of the sensitive radiation linear resin composition. <Preparation of Sensitive Radiation Linear Resin Composition> The sensitive radiation linear resin composition can be obtained by mixing [A] polymer, [B] polymer, [C] radiation sensitive linear acid generator in a specific ratio, for example, in an organic solvent. And modulation with arbitrary components. Further, the sensitive radiation linear resin composition can be used in a state of being dissolved or dispersed in a suitable organic solvent. The content ratio of the polymer [A] is preferably 1 part by mass to 15 parts by mass, more preferably 2 parts by mass to 1 part by mass, based on 100 parts by mass of the [B] polymer. [Examples] Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited by the Examples -46-201211688. <[A] Synthesis of Polymer> [Synthesis Example 1] 10.4 g (30 mol%) of a monomer represented by the following formula (M-1) and 19.6 g (70 mol%) of a monomer represented by the formula (M-4) The solution was prepared by dissolving in 30 g of methyl ethyl ketone and then pouring 0.91 g of 2,2'-azobis(isobutyronitrile). Next, a 200 mL three-necked flask in which 30 g of methyl ethyl ketone was poured was subjected to nitrogen blowing for 30 minutes, and then heated to 80 ° C while stirring with the reaction vessel, and previously prepared by dropwise addition using a dropping funnel over 3 hours. Monomer solution. The polymerization was carried out for 6 hours by starting the dropwise addition as the polymerization starting time. After the completion of the polymerization, the solution was cooled to 30 ° C or less by water cooling, and after the reaction solution was pipetted into a 1 L separatory funnel, the polymerization solution was uniformly diluted with 90 g of n-hexane, and 3 60 g of methanol was poured and mixed. Next, 20 g of distilled water was poured, and the mixture was stirred and allowed to stand for 30 minutes. Subsequently, the lower layer was recovered to become a propylene glycol monomethyl ether solution containing the polymer (A-1). The polymer (A-1) had a Mw of 5,900 and a Mw/Mn of 1.58' in a yield of 68%. As a result of 13C_NMR analysis, the structural unit (I) obtained by (M-1) and the structural unit (I) obtained by (μ-4) were contained in a ratio of 3 1 : 69 (mol%). Further, 13C-NMR analysis was carried out using a nuclear magnetic resonance apparatus (Sakamoto Electronics Co., Ltd., JNM-EX2 70). -47- 201211688 【化1 9】

ο cf3 F3C

(Μ-4) [Synthesis Examples 2 to 10] The respective polymers were synthesized in the same manner as in Synthesis Example 1, except that the monomers described in Table 1 were blended in a specific amount. Further, the Mw, Mw/Mn, yield (%) of each obtained polymer, and the content ratio of the structural unit obtained by each monomer in each polymer are shown in Table 1. Further, the monomer used in the synthesis of each [A] polymer is shown below. [化2 0]

48- 201211688

<[B] Synthesis of Polymer> [B] The monomer used in the synthesis of the polymer is shown below. [Chem. 2 1]

(M-17) (M-18) [Synthesis Example 11] -49-201211688 A monomer represented by the following formula (Μ-ll): 12.9 g (50 mol%) and a formula represented by the formula (Μ-1 6 ) The solution 1 7. 1 g (50 mol%) was dissolved in 60 g of methyl ethyl ketone, followed by pouring 1.77 g of dimethyl azobisisobutyronitrile to prepare a solution. Next, a 200 mL three-necked flask in which 30 g of methyl ethyl ketone was poured was subjected to nitrogen blowing for 30 minutes, and then heated to 8 CTC while stirring the reaction vessel, and a previously prepared monomer solution was added dropwise over 3 hours using a dropping funnel. The polymerization was carried out for 6 hours by starting the dropwise addition as the polymerization initiation time. After the completion of the polymerization, the polymerization solution was cooled to 30 ° C or lower by water cooling, poured into 600 g of methanol, and the white powder was separated by filtration. The filtered white powder was washed twice with a solution of 150 g of methanol, and then filtered again, and dried at 50 ° C for 17 hours to obtain a white powdery (8-1) polymer. The polymer (8-1) was 1,900, Mw/Mn was 1.35, and the yield was 80%. As a result of 13C-NMR analysis, the structural unit (IV) obtained by the structural units (III) and (M-16) obtained by (M-1 1 ) was 49:51 (mol%). [Synthesis Example 1 2] 12.57 g (35 mol%) of the monomer represented by the following formula (M-12), 5.13 g (15 mol%) of the monomer represented by the formula (M-15), and the formula (M-17) The monomer 12.3 g (50 mol%) was dissolved in 60 g of methyl ethyl ketone, and then 1-1 mM of dimethylazobisisobutyronitrile was poured to prepare a solution. Next, a 200 mL three-necked flask into which 30 g of methyl ethyl ketone was poured was subjected to nitrogen blowing for 3 minutes, and then heated to 80 ° C while stirring the reaction vessel, and a previously prepared single was added dropwise over 3 hours using a dropping funnel. Body solution. The polymerization was carried out for 6 hours by starting the dropwise addition as the polymerization starting time. After the completion of the polymerization, the polymerization solution -50 - 201211688 was cooled to 30 ° C or lower by water cooling, and poured into 600 g of methanol to filter out the white powder. The filtered white powder was washed twice with a solution of 150 g of methanol, and then filtered again, and dried at 50 ° C for 1 hour to obtain a white powdery (B-2) polymer. The polymer (B-2) had a Mw of 5,800, a Mw/Mn of 1.37 and a yield of 68%. As a result of 13C-NMR analysis, the structural unit obtained by (M-12), the structural unit obtained by (M-15), and the structural unit (IV) obtained by (M-17) were 3 3 : 16 : 5 1 ( mol% ). [Synthesis Example 1 3] 1.73 g (40 mol%) of the monomer 1 represented by the following formula (M-13), 2.62 g (10 mol%) of the monomer represented by the formula (M-14), and 15.66 g (50 mol%) of the monomer represented by M-18) was dissolved in 60 g of methyl ethyl ketone, followed by pouring 9.2 mg of dimethylazobisisobutyronitrile to prepare a solution. Next, a 200 mL three-necked flask in which 30 g of methyl ethyl ketone was poured was subjected to nitrogen blowing for 30 minutes, and then heated to 80 ° C while stirring the reaction vessel, and a previously prepared single was added dropwise over 3 hours using a dropping funnel. Body solution. The polymerization was carried out for 6 hours by starting the dropwise addition as the polymerization starting time. After the completion of the polymerization, the polymerization solution was cooled to 30 ° C or lower by water cooling, and poured into 600 g of methanol to filter out the white powder. The filtered white powder was washed twice with a slurry of 150 g of methanol, and then filtered again, and dried at 50 ° C for 17 hours to obtain a white powdery (B-3) polymer. The polymer (B-3) had a Mw of 7,200 Å Mw/Mn of 1 to 41 and a yield of 75%. As a result of 13C-NMR analysis, the structural unit obtained by (M-13), the structural unit obtained by (M-14), and the structural unit (IV) obtained by (M-18 -51 - 201211688) were 40 : 1 0 : 50 ( mol% ). [Table 1] Monomer structure unit yield (%) M w M w /Μ η Surface ratio (mol%) Content ratio (mol%) Synthesis Example 1 A-1 M-1/M-4 30/ 70 31/69 68 5,900 1.58 Synthesis Example 2 A-2 M-1/M-4 60/40 61/39 65 5,700 1,52 Synthesis Example 3 A-3 M-1 100 100 60 6,1〇〇1.55 Synthesis Example 4 A-4 Μ-2/Μ -5 70/30 68/32 70 6,300 1.50 Synthesis Example 5 A-5 Μ-2/Μ-3 70/30 72/28 73 6,200 1.51 Synthesis Example 6 A-6 Μ -3/Μ-5 70/30 68/32 79 6,500 1.42 Synthesis Example 7 A-7 Μ-3 100 100 79 6,700 1.49 Synthesis Example 8 A-8 Μ-4/Μ-6/Μ-7 50/40/ 10 52/39/9 75 6,300 1.45 Synthesis Example 9 A-9 Μ-1/Μ-8/Μ-9 15/25/60 16/26/58 60 4,900 1.39 Synthesis Example 10 A-10 Μ-4/Μ -10 60/40 60/40 47 4,000 1.35 Synthesis Example 11 B-1 M-ll/M-16 50/50 49/51 80 6,900 1.35 Synthesis Example 12 B-2 M-12/M-15/M-17 35/15/15 33/16/51 68 5,800 1.37 Synthesis Example 13 B-3 M-13/M-14/M-18 40/10/50 40/10/50 75 7,200 1.41 <sensitive radiation linear resin composition Modulation> The [C] radiation sensitive linear acid generator, acid diffusion controlling agent and solvent used in the preparation of the sensitive radiation linear resin composition are as follows. <[C]sensitive radiation linear acid generator> A compound represented by the following formula [Chemical 2 2]

52- 201211688

<[D] Acid Diffusion Control Agent> A compound represented by the following formula

<[E] solvent> E-1: propylene glycol monomethyl ether-53-201211688 E-2: cyclohexanone E-3: γ-butyrolactone [Example 1] Mixed as a [Α] polymer ( Α-1) 3 parts by mass, (Β-1) 1 〇〇 by mass of [Β] polymer, (C-1) 10.8 parts by mass of [C]sensitive radiation linear acid generator, as [d] (0-1) 4.3 parts by mass of the acid diffusion controlling agent, (£-1) 2,185 parts by mass, (Ε-2) 935 parts by mass, (Ε_3) 30 parts by mass of the solvent diffusion controlling agent Linear Resin Composition [Examples 2 to 13 and Comparative Examples 1 to 2] Various photosensitive radiation linear resin compositions were prepared in the same manner as in Example 1 except that the components described in Table 2 were blended in a specific amount. [Table 2] [A] component [B 丨] Polymer 151: Silver ray generator 1 [D-face preparation 1 solvent type containing fl: (mass parts) Type ft (quality portion) Brewing content mm) Mm disk (mass parts) lion, containing (mass parts) S Example 1 A-1 3 Β-1 100 C-1 10.8 Dl 4·3 1 E-1/E-2/E-3 2,185/935 /30 贲Example 2 A-2 3 Β-1 100 C-1 10.8 Dl 4.3 EI/E-2/E-3 2,185/935/30 寅3 3-3-3 Β-1 100 C- 1 10.8 Dl 4.3 E-1/E-2/E-3 2,185/935/30 Example 4 A-4 3 Β-1 100 ci 10 Dl 4.3 E-1/E-2/E-3 2,185/935 /30 Example 5 A-5 3 Β-1 100 c-1 10.8 Dl 4.3 E-1/E-2/E-3 2,185/935/30 Example 6 A-6 3 Β-1 100 C-1 10 · 8 Dl 4.3 E-1/E-2/E-3 2,185/935/30 Example 7 A-7 3 Β-1 100 CL 10.8 Dl 4.3 E-1/E-2/E-3 2,185/935/ 30 Bao Shi Example 8 A-8 3 Β-1 100 C-1 10.8 Dl 4.3 E-1/E-2/E-3 2,185/935/30 Example 9 A-4 3 Β-2 100 C-2 9.0 D-2 1.0 E-1/E-2/E-3 2^50/965/30 Example 10 A_5 3 Β-2 100 C-2 9.0 D-2 1.0 ί E-1/E-2/E- 3 2^60/965/30 Example 11 A-6 3 Β-2 100 C-2 9.0 D-2 1.0 E-1/E-2/E-3 2^50/965/30 A-7 3 Β -3 100 C~3 11.5 D-3 ' 0.7 E-1/E-2/E-3 2^50/965/30 — A-8 3 Β-3 100 C-3 11.5 D-3 0.7 E-1/E- 2/E-3 2^50/965/30 Comparative Example 1 A-9 3 Β-1 100 ~ci 10.8 Dl 4.3 E-1/E-2/E-3 2,185/935/30 Comparative Example 2 A-10 3 Β-1 100 10.8 Dl 4.3 E-1/E-2/E-3 2485/935/30 <Formation of resist pattern> Using a rotary applicator (CLEAN TRACK Lithius Pro i, East-54-201211688 Beijing An electronic antireflective film forming agent (Nissan Chemical Co., Ltd., ARC66) was applied onto the surface of the wafer, and then heated at 205 ° C for 60 seconds to form an organic antireflection film having a film thickness of 105 nm. On the surface of the substrate, a variety of radiation sensitive linear resin compositions were applied by spin coating using a Clean Track (Tokyo Electronics Co., Ltd., ACT12), and soft-baked at 100 ° C for 60 seconds on a hot plate. A film thickness Ο.ΙΟιη resist film. Next, using an ArF liquid immersion exposure apparatus (NSR-S610C, NIKON Seiki Co., Ltd.), exposure was carried out under optimal optical conditions under the optical conditions of NA = 丨.3, quadrupole. The exposure system used a 1./4x projection scanner (NSR-S610C, NIKON Seiki Co., Ltd.), and the size on the grating was 0.220 μm chrome / 0.44 0 μιη pitch, and the mask bias was Onm. Thereafter, the film was subjected to post-exposure baking at a temperature shown in Table 3 for 60 seconds on a hot plate, and then developed with butyl acetate at 23 ° C for 30 seconds, and washed with 4-methyl-2-pentanol solvent. After the leap second, it is dried to form a negative resist pattern. &lt;Evaluation&gt; The following evaluation was performed for each of the formed resist patterns. The results are shown in Table 3 [sensitivity (mJ/cm2)] so that the diameter of the hole pattern after the reduction of the projection exposure becomes 〇. 55 μιη by the method of permeating the water to expose the mask having the dot pattern to form the film. The hole pattern is an exposure amount of a hole having a diameter of 0.05 5 μm as an optimum exposure amount 'and the optimum exposure amount is used as a sensitivity (mj/cm 2 ). In addition, the -55-201211688 length measurement system is based on a scanning electron microscope (Hitachi Hi-Tech Co., Ltd., at a time when the sensitivity is below 16 (mJ/cm2), the cross-sectional shape is observed using Hitachi High-Tech Co., Ltd. S-4800. The cross-sectional shape of the 0·05 5μιη hole pattern. Measure the line width Lb of the resist pattern and the line width La of the upper part of the film, and record it as “A” in the range of 0.9; S 1 · 1 (judgment) For the good external note, it is "B" (it is judged to be bad). [Circularity] Among the above-mentioned optimum exposure amounts, the measurement length SEM (曰立 ' CG4000 ) ' is used to observe the upper surface of the pattern from the upper part of the pattern. The hole pattern of 0 5 5 μιτι is measured. The deviation of the diameter is measured at any point. When the deviation is 〇·〇〇9μιη or less, it is judged as “when it is 0.009μπι, it is judged as “defective”. [Resolvability] The use has a dot shape. In the pattern mask, the minimum size of the hole obtained when the exposure amount is increased by the liquid immersion water is judged as "good" when the hole size is less than 0.050 μm, and 〇〇5 〇 μη^ "poor". CG4000). For the sensitivity of the evaluation of the middle of the medium s ( La/Lb)), in the range of high-tech company's anti-corrosion coating, and good evaluation by 3σ, super exposure, and the minimum size of the hole is judged as -56- 201211688 [Table 3] PEB CC) Sensitivity ( mT/cm2) cross-sectional shape circular resolution (β m) Example 1 105 14.5 A 0.0056 0.037 Example 2 105 14.0 A 0.0058 0.038 Example 3 105 14.0 A 0.0076 0.039 Example 4 105 14.5 A 0.0083 0.039 Example 5 105 15.0 A 0.0087 0.037 Example 6 105 15.0 A 0.0071 0.038 Example 7 105 14.5 A 0.0074 0.033 Example 8 105 20.0 A 0.0089 0.034 Example 9 90 13.5 A 0.0065 0.040 Example 10 90 14.0 A 0.0070 0.039 Example 11 90 13.5 A 0.0068 0.039 Example 12 95 15.0 A 0.0069 0.041 Example 13 95 15.5 A 0.0068 0.040 Comparative Example 1 105 16.0 B 0.0107 0.052 Comparative Example 2 105 16.5 B 0.0111 0.052 As can be seen from Table 3, the pattern forming method of the present invention is used. The composition has excellent sensitivity, and the formed resist pattern has excellent cross-sectional shape, circularity, and resolution. [Industrial Applicability] The present invention provides a method for forming a groove pattern or a hole pattern which is excellent in lithographic properties such as sensitivity, cross-sectional shape, circularity, and resolution as a liquid immersion exposure, and Sensitive radiation linear resin composition. -57-

Claims (1)

201211688 VII. Patent application scope: 1. A method for forming a groove pattern or a hole pattern, which comprises a groove pattern or a hole pattern formation method of the following steps: (1) a sensitive radiation linear resin composition a step of forming a resist film on the substrate, (2) an exposure step of irradiating the resist film with radiation through the mask, and (3) a developing step of developing the exposed resist film The above-mentioned sensitive radiation linear resin composition contains: [A] a polymer having a structural unit of an acid dissociable group in a proportion of 1 〇 mol% or less, [B] a content ratio of a structural unit having an acid dissociable group More than 10 mol% of the polymer, and [C] a radiation-sensitive linear acid generator, and the developing solution in the above (3) development step contains 80% by mass or more of an organic solvent. 2. The method for forming a pattern according to claim 1, wherein the [A] polymer has a higher fluorine content than the [B] polymer. 3. The method for forming a pattern according to the first aspect of the invention, wherein the organic solvent is at least one organic solvent selected from the group consisting of an ether solvent, a ketone solvent, and an ester solvent. 4. The method of forming a pattern according to the first aspect of the invention, wherein the [A] polymer has a structural unit (I) represented by the following formula (1) and a structural unit represented by the following formula (2) (Π) The group selected is at least -58- 201211688 - a structural unit '[1] R1 Ο (1) Ο R2 \ (In the formula (1), 'R1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group' R2 is a linear or branched alkyl group having 1 to 6 carbon atoms or a carbon number. 4~20 0% alicyclic hydrocarbon group 'but 'the at least one part of the hydrogen atom of the above alkyl group and the alicyclic hydrocarbon group is substituted by a fluorine atom) 'Chemical 2】 R3 (In the formula (2), R3 is a hydrogen atom, a methyl group or a trifluoromethyl group, R4 is a (m+1)-valent linking group, and X is a divalent linking group having a fluorine atom. R5 is a gas atom or a monovalent group. The organic group, m is an integer of 1 to 3, but when 'm is a plural number, the plurality of X and R5 may be the same or different. 5. The pattern forming method according to claim 1, wherein the acid dissociable group of the [B] polymer has a chain hydrocarbon group or a monocyclic or polycyclic alicyclic hydrocarbon group. -59- 201211688 6. A sensitive radiation linear resin composition comprising the following steps of forming a trench pattern or a hole pattern: (1) applying a radiation sensitive linear resin composition onto a substrate to form a resist a step of filming, (2) an exposure step of irradiating the resist film with radiation through the mask, and (3) a developing step of developing the exposed resist film, and the image forming in the above step (3) The liquid contains 80% by mass or more of an organic solvent, and is characterized in that the sensitive radiation linear resin composition contains: [A] a polymer having an acid dissociable group having a structural unit content of 10 mol% or less, [B] having The structural unit of the acid dissociable group contains a polymer having a ratio of more than 10 mol%, and the [C] sensitive radiation linear acid generator. -60- 201211688 IV. Designated representative map: (1) The representative representative of the case is: None. (II) Simple description of the symbol of the representative figure: None 201211688 V If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: none