TW201232167A - Pattern forming method and radiation-sensitive resin composition - Google Patents

Abstract

The purpose of the present invention is to provide: a method for forming trench patterns and/or hole patterns, which is capable of forming patterns that minimize the occurrence of roughness on the upper patterned surface of a resist film, and that have excellent resolution, pattern size uniformity, cross-sectional shape, etc.; and a radiation-sensitive resin composition. The present invention is a method for forming trench patterns and/or hole patterns which includes, (1) a resist film forming step in which a radiation-sensitive resin composition is applied on a substrate, (2) an exposure step in which the resist film is exposed, and (3) a development step in which the exposed resist film is developed with a developing solution; said method being characterized in that the developing solution contains at least 80 mass % of an organic solvent, and the radiation-sensitive resin composition contains, [A] a polymer that includes a structural unit containing an acid dissociable group, and the polarity of which increases due to the effect of acid, [B] radiation-sensitive acid-generating body, and [C] an acid diffusion control body having a polar group.

Description

201232167 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of forming a pattern 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 photoresist 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 photoresist pattern having a line width of about 90 nm, but in the future, a finer pattern is required. A means for forming a finer pattern can be used, and a technique of using an organic solvent having a polarity lower than that of an alkaline aqueous solution to improve resolution is known (refer to Japanese Laid-Open Patent Publication No. 2000-99953). Thus, the use of an organic solvent in the developing solution can improve the optical contrast when forming a groove pattern or a hole pattern with respect to the use of an aqueous alkali solution. However, in the developing step of using the organic solvent in the developing solution, the acid generated by the exposed portion of the resist film diffuses to the unexposed portion, resulting in a problem that the dissolution of the exposed portion and the unexposed portion is insufficient. Therefore, in order to suppress the undesirable chemical reaction in the unexposed area of the photoresist film, the acid diffusion controlling agent is formulated, but the poor solubility to the organic solvent is insufficient, and even if the acid diffusion controlling agent is formulated, the upper surface of the pattern is still rough. unpleasant sight. In the case of prebaking (PB), the evapotranspiration of the acid diffusion controlling agent will produce a Tt〇p shape in the groove pattern, and the missing contact pattern will result in a pattern size unevenness. . -5- 201232167 In particular, in the formation method of the negative-type photoresist groove pattern and/or the hole pattern of the above-mentioned developing solution using the organic solvent, the above-mentioned defective optimal sensitivity radiation linear resin composition and use have not been found. The imaging solution, and the combination of them. [PRIOR ART DOCUMENT] [Patent Document 1] International Publication No. 04/06 8242 [Patent Document 2] JP-A-2000-199953 SUMMARY OF INVENTION [Summary of the Invention] [Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and an object thereof is to provide a basic characteristic of sensitivity and the like in the lithography step, while suppressing roughness, resolution, and pattern size on the upper surface of the pattern of the photoresist film. A method of forming a groove pattern and/or a hole pattern which is excellent in uniformity and cross-sectional shape, and a radiation-sensitive linear resin composition. [Means for Solving the Problem] The invention for solving the above-mentioned problems is a method for forming a pattern, which includes a method of forming a groove pattern and/or a hole pattern of the following steps (1) to (3): (1) a step of forming a photoresist film on the substrate by applying a radiation sensitive linear resin composition;

S 201232167 (2) an exposure step of exposing the photoresist film; and (3) a developing step of developing the exposed photoresist film by a developing solution; characterized in that the developing solution contains 80% by mass or more of the organic solvent, the above-mentioned radiation-sensitive linear resin composition contains: [A] a polymer having a structural unit containing an acid-dissociable group and having an increased polarity by an action of an acid (hereinafter also referred to as "[ A] polymer"), [B] sensitive radiation linear acid generator (hereinafter also referred to as acid generator) and [C] acid diffusion control body having polar group (hereinafter also referred to as "[C] acid diffusion control body"). According to the method of forming the pattern of the present invention, the occurrence of roughness in the upper portion of the resist pattern can be suppressed. This is because the [C] acid diffusion control body contained in the radiation sensitive linear resin composition used in the formation method has a polar group, and therefore the solvent resistance of the exposed portion of the photoresist film to the organic developing solution is increased. Further, the [C] acid diffusion control system is interposed between polar groups and easily interacts with a resin or other components, so that it is difficult to evade in a high-temperature treatment step such as PB. Therefore, when the pattern formation method is employed, the concentration distribution of the [C] acid diffusion control body in the film thickness direction of the photoresist film is less likely to be formed, so that a pattern having excellent cross-sectional shape and pattern size uniformity can be formed. . The [C] acid diffusion controlling body is preferably a nitrogen-containing compound represented by the following formula (1). 201232167 【化1】 R1 il (1) R〆\R3 (In the formula (1), R1, R2 and R3 are each independently a linear or branched alkyl group having a carbon number of 1 to 10, and a carbon number of 3 to 2 a cycloalkyl group of 0 or an alkoxycarbonyl group, but any two of R^R3 are bonded to each other to form a heterocyclic ring together with the nitrogen atom to which they are bonded. However, R1, R2, R3 or the above heterocyclic hydrogen At least one of the atoms is replaced by a polar group). The [C] acid diffusion control system has a moderate basicity when it is a nitrogen-containing compound represented by the above formula (1), and is suitable for suppressing diffusion of an acid generated by an acid generator in the resist film by exposure. Further, at least one of R1, R2, R3 or a hydrogen atom of the above heterocyclic ring in the above formula (1) is substituted with a polar group. Therefore, according to the formation method of the pattern, the photoresist film at the time of pattern formation can be suppressed. The roughness of the surface occurs, and the uniformity of resolution, cross-sectional shape, and pattern size is superior. The above polar group is preferably a hydroxyl group or a carboxyl group. When the above polar group is a hydroxyl group or a carboxyl group, it is interposed between a polar group and a lactone group or a polar group in the polymer, so that evapotranspiration in PB can be suppressed. As a result, when the pattern formation method is employed, the roughness of the surface of the photoresist film can be suppressed, and the uniformity of the resolution, the cross-sectional shape, and the pattern size is further improved. Any one of the above R1, R2 and R3 is preferably represented by the following formula (2).

S -8- 201232167 【化2】

R4--R6 (2) R5 (In the formula (2), R4, R5 and R6 are each independently a linear or branched alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 4 to 12 carbon atoms. However, R4 and R5 are bonded to each other to form a cycloalkylene group having a carbon number of 4 to 12 together with the carbon atoms to which they are bonded. * indicates a moiety bonded to a nitrogen atom). When R1, R2 or R3 has the structure represented by the above formula (2), the affinity of the [C] acid diffusion controlling agent with an acid is improved, and the acid produced by the [B] sensitive radiant acid product can be quickly captured. Further, since the molecular weight is increased, it is difficult to evade when PB is used. The acid dissociable group of [A] polymer preferably has an alicyclic group. The [A] polymer has an alicyclic group and can improve the transparency of the photoresist film to an ArF excimer laser or the like. Therefore, when the pattern is formed, a pattern having more excellent resolution can be formed. In the above (2) exposure step, it is preferred to perform a plurality of exposures. Thus, according to the formation method of the pattern, the resolution is high and a finer pattern can be formed. The present invention also includes a radiation sensitive linear resin composition comprising a radiation sensitive linear resin composition for forming a groove pattern and/or a pore pattern of the following steps (1) to (3), -9-201232167 (1) a step of forming a photoresist film on a substrate by applying a radiation sensitive linear resin composition; (2) an exposure step of exposing the photoresist film; and (3) exposing the film by a developing solution The developing step of developing the photoresist film; wherein the developing solution contains 80% by mass or more of an organic solvent, and the sensitive radiation linear resin composition contains: [A] a structural unit having an acid dissociable group And a polymer having an increased polarity by an action of an acid, a [B] sensitive radiation linear acid generator, and [C] an acid diffusion controlling body having a polar group. [Effect of the Invention] According to the method for forming a pattern of the present invention, the basic characteristics of the sensitivity and the like are satisfied, and the occurrence of roughness of the upper surface of the pattern of the photoresist film can be suppressed, and the resolution, pattern size uniformity, and profile can be formed. Excellent shape such as shape. This can be used for various electronic device configurations such as semiconductor devices and liquid crystal devices that require further miniaturization. [Formation of the Invention] <Method for forming groove pattern and/or hole pattern> The present invention relates to a method for forming a groove pattern and/or a hole pattern, which comprises the following (1) to (3) The method for forming the groove pattern and/or the hole pattern of the step: (1) forming the sensitive radiation linear resin composition on the substrate

S -10- 201232167 a step of a photoresist film; (2) an exposure step of exposing the photoresist film; and (3) an imaging step of developing the exposed photoresist film by a developing solution The image forming liquid in the (3) developing step contains 80% by mass or more of an organic solvent, and the sensitive radiation linear resin composition contains: [A] having a structural unit containing an acid dissociable group, and The acid acts to increase the polarity of the polymer, [B] the sensitive radiation linear acid generator, and [C] the acid diffusion control body having a polar group. Each step is detailed below. [Step (1)] In this step, the composition for use in the present invention is applied onto a substrate to form a photoresist film. As the substrate, a conventional substrate such as a tantalum wafer or an aluminum-coated wafer can be used. Further, an organic or inorganic antireflection film disclosed in, for example, JP-A-6-245-2, JP-A-59-93448, or the like can be formed on the substrate. The coating method is, for example, spin coating, cast coating, roll coating, or the like. Further, the film thickness of the formed photoresist film is usually 0.0 1 μηι to 1 μηη, preferably Ο.ΟΙμιη to 0.5 μιη.

After coating the composition, the solvent in the coating film may be volatilized by pre-baking (Ρ 可视) as needed. The heating condition of PB can be appropriately selected depending on the composition of the composition, but it is usually 30 ° C to 20 (TC, preferably 50. (: ~ 150 ° C -11 - 201232167) in order to prevent the alkali contained in the environmental atmosphere A protective film disclosed in, for example, Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. 5-8 8 8 9 8 can be provided on the photoresist layer. Further, in order to prevent the acid generator from flowing out of the photoresist layer, A liquid immersion protective film disclosed in, for example, JP-A-2005-352384 can be provided on the photoresist layer. Further, these techniques can be employed. [Step (2)] This step is formed for the step (1). The desired area of the photoresist film is exposed by a reticle of a specific pattern and, if necessary, by a liquid immersion liquid. For example, for a desired area, there is an Iso line. The pattern mask can reduce the projection exposure to form an equal groove pattern. Moreover, the exposure system can be performed twice or more depending on the desired pattern and the mask pattern. When two or more exposures are performed, Good for continuous exposure. For multiple exposures, for example, in the desired area The line-and-pitch pattern mask performs the first reduction projection exposure, and then performs the second reduction projection exposure on the exposure portion after the first exposure, so that the lines are crossed. The first exposure unit and the second exposure unit Preferably, the exposure portions are orthogonal to each other, and a circular contact hole pattern can be easily formed in the unexposed portion surrounded by the exposed portion by orthogonality. Further, the liquid immersion liquid used for exposure, for example, water or Fluorine-based inert liquid, etc. The liquid immersion liquid is transparent to the exposure wavelength, and the deformation of the optical image projected onto the film is suppressed to a minimum. Therefore, it is preferable that the temperature coefficient of the refractive index is as small as possible. However, in particular, when the exposure light source is ArF excimer laser light (wavelength: 193 nm), in addition to the above viewpoint, it is preferable to use water from the viewpoint of easiness of handling and ease of handling.

S -12- 201232167 Add a few additives to reduce the surface tension of water and increase the interfacial activity. Preferably, the additive does not dissolve the photoresist layer on the wafer and does not affect the optical coating under the lens. The water used is preferably distilled water. The radiation used for the exposure is appropriately selected in combination with the type of the [B] acid generator, for example, ultraviolet rays, far ultraviolet rays, X rays, charged particle beams, and the like. Among these, it is preferably a far ultraviolet ray represented by an ArF excimer laser (wavelength 193 nm) 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 in accordance with the composition of the composition, the type of the additive, and the like. The photoresist pattern forming method of the present invention may have a plurality of exposure steps, and the plurality of exposures 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 preferable to perform post-exposure baking (PEB) after exposure. The dissociation reaction of the acid dissociable group in the composition can be carried out smoothly by performing PEB'. The heating condition of PEB is usually from 30 ° C to 200 °. (:, preferably 50. (: ~1 7 〇 ° C ° [Step (3)] This step is a negative-type image containing 80% by mass or more of an organic solvent after exposure in the step (2) The liquid is developed to form a groove pattern and/or a hole pattern. The negative-type developing solution refers to a developing solution that selectively dissolves and removes the low-exposure portion and the unexposed portion. The organic solvent is preferably at least one organic solvent selected from the group consisting of an alcohol solvent, an ether solvent, a ketone organic solvent, a guanamine solvent, an ester organic solvent, and a hydrocarbon solvent. For example, there are methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, n-pentanol, isoamyl alcohol, 2-methylbutanol, second pentane Alcohol, third pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, second hexanol, 2-ethylbutanol, second heptanol, 3-heptanol, n-octanol , 2-ethylhexanol, second octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-nonanol, second-undecyl alcohol, trimethyl decyl alcohol, second -tetradecanol, second-ten a monoalcoholic solvent such as heptaol, decyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol or diacetone alcohol; ethylene glycol; 2-propanediol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2 - a polyol solvent such as ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol or tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol single Propyl 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, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, a polyhydric alcohol partial ether solvent such as dipropylene glycol monoethyl ether or dipropylene glycol monopropyl ether. Examples of the ether solvent include an anthrone solvent such as diethyl ether, dipropyl ether, dibutyl ether or diphenyl ether, such as acetone or methyl b. Ketone, methyl n-propyl ketone, -14-

S 201232167 methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl A ketone solvent such as anthrone ketone 'cyclopentanone' cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, etidylacetone or acetophenone. The guanamine-based solvent is, for example, N,N'-dimethylimidazolidinone, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamidine Amine, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, and the like. Examples of the ester solvent include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, n-butyl acetate, isobutyl acetate, and acetic acid. Second butyl ester, isoamyl acetate, n-amyl acetate, second amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate Ester, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-decyl acetate, methyl acetoxyacetate, ethyl acetoxyacetate, ethylene glycol monomethyl ether acetate, acetic acid Alcohol 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, acetic acid Propylene glycol monoethyl ether ester, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxy acetate Tri-diol 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. -15- 201232167 Hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane , an aliphatic hydrocarbon solvent such as cyclohexane or methylcyclohexane; benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropyl An aromatic hydrocarbon solvent such as benzene benzene diethyl ether, isobutyl benzene, triethyl benzene, diisopropyl benzene or n-pentyl naphthalene. Among these, n-butyl acetate, isoamyl acetate, n-amyl acetate, methyl ethyl ketone, methyl n-butyl ketone, and methyl n-amyl ketone are preferred. These organic solvents may be used singly or in combination of two or more. The content of the organic solvent in the developing solution is 80% by mass or more, preferably 90% by mass or more. It is preferably 99% by mass or more. The organic solvent containing 80% by mass or more in the developing solution can provide a good developing property and a pattern excellent in microscopic properties. Further, examples of the components other than the organic solvent include water, an oxime oil, and a surfactant. The developer may be added with an appropriate amount of surfactant as needed. The surfactant is, for example, an ionic or nonionic fluorine-based surfactant and/or a ruthenium-based surfactant. The developing method includes, for example, a method of immersing a substrate in a tank filled with a developing liquid for a predetermined period of time (immersion method), a method of raising the developing liquid to the surface of the substrate by surface tension, and performing development for a certain period of time (paddle stirring method). a method of spraying a developing solution onto a surface of a substrate (spraying method), scanning a developing solution discharge nozzle at a constant speed, and continuously discharging the developing solution onto a substrate rotating at a constant speed (dynamic coating method) Wait. The pattern formation is preferably after the development of the step (3), and the -16-S. 201232167 photoresist film is preferably washed with a washing liquid. Moreover, the washing liquid in the washing step can also use an organic solvent, and the generated dross can 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 or an ester solvent is preferred, and an alcohol solvent having a carbon number of 6 to 8 is more preferred. The one-valent alcohol having 6 to 8 carbon atoms is, for example, a linear, branched or cyclic one-valent alcohol such as 1-hexanol, 1-heptanol, 1-octanol or 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, 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 particularly preferably 3% by mass or less. When the water content is 1% by mass or less, good development characteristics can be obtained. Further, an interface active agent to be described later may be added to the washing liquid. The method of the cleaning treatment, for example, a method of discharging the washing liquid onto a substrate rotating at a constant speed (spin coating method), a method of immersing the substrate in a tank filled with the washing liquid for a predetermined period of time (dipping method), and a substrate A method of spraying a washing liquid on a surface (spraying method) or the like. <Mens radiation linear resin composition> The radiation sensitive linear resin composition used in the present invention contains [A] polymer, [B] acid generator, and [C] acid diffusion controller. [A] The polymer contains an acid-dissociable group which is dissociated by the action of an acid generated by the [B] acid generator. Results [A] The polarity of the polymer increased, and the exposure portion was difficult.

-17- S 201232167 Increased solubility. The sensitive radiation linear resin composition used in the present invention contains the [C] acid diffusion control body, thereby suppressing the diffusion phenomenon of the acid generated by the [B] acid generator from diffusing into the photoresist film, and suppressing the unexposed region. Chemical reaction. Further, since the [C] acid diffusion controlling body has a polar group, the poor solubility in the negative developing solution of the exposed portion increases, and the dissolution of the exposed portion/unexposed portion increases. As a result, the solvent resistance of the upper portion of the pattern to the organic developing solution is increased, and the roughness of the surface of the photoresist film can be suppressed. Further, the composition may contain other optional components without affecting the effects of the present invention. Each component is detailed below. <[A].Polymer> [A] The polymer contains a structural unit having an acid-dissociable group and a polymer having an increased polarity due to the action of an acid. [Structural unit (I)] The [A] polymer is preferably a structural unit (I) represented by the following formula (3). [Chemical 3] R7

(In the formula (3), 'R7 is a hydrogen atom, a methyl group or a trifluoromethyl group. The RP is an acid dissociable group.) The acid dissociable group represented by Rp is preferably represented by the following formula (4): - 201232167 Group. RP1 — C — RP3 (4) (In the formula (4), Rpl is an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. The Rp2 and Rp3 systems are each independently An alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. Rp2 and Rp3 are bonded to each other to form a divalent fat having 4 to 20 carbon atoms together with the carbon atoms to which they are bonded. Cyclic hydrocarbyl). The alkyl group having 1 to 4 carbon atoms represented by Rpl, Rp2 and Rp3, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl , third butyl, and the like. a one-valent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by Rpl, Rp2 and Rp3, for example, a polycyclic alicyclic group having a bridged skeleton such as an adamantane skeleton or a norbornane skeleton; having a cyclopentane and a cyclohexane a monocyclic alicyclic group of a cycloalkane skeleton such as an alkane. Further, these groups may be substituted with, for example, one or more of linear, branched or cyclic alkyl groups of carbon number. In these, Rp is an alkyl group having 1 to 4 carbon atoms, and Rp2 and Rp3 are bonded to each other to form an adamantane skeleton or a cycloalkane skeleton together with a carbon atom bonded thereto; and a divalent group is preferred. The structural unit (I) has, for example, a structural unit represented by the following formula (1 -1 ) to (1 -4 ). -19- 201232167 【化5】

(In the formulae (1-1) to (1-4), R7 is synonymous with the above formula (3). Rpl, Rp2 and Rp3 are the same as the above formula (4). An integer of the np system.) The structural unit indicated by the following formula is, for example, a structural unit represented by the following formula. -20- 201232167 【化6】

R7 R7 R7

Ο

R7 R7

R7

O

O R7

0 O

-21 - 201232167 【化7】 R7 R7 R7

(wherein R7 is synonymous with the above formula (3)) [A] In the polymer, the content ratio of the structural unit (I) is relative to the constitution

-22- S 201232167 [A] The total amount of structural units (i) of the full structural unit of the polymer, cold 20 mol % ~ 80 mol %, more preferably 25 mol % ~ 70 mol %. Further, the polymer may have one or more structural units (I). Providing a monomer of the structural unit (I), for example, a monomer having an acid-dissociable group having a monocyclic alicyclic group such as an i-alkyl ester, a 2-2 - ring-based vinegar, and a 2-yard group - A 2-second ring-based vinegar or the like having a polycyclic group of acid-dissociable groups. [Structural unit (II)] The [A] polymer is preferably a constituent unit f having a lactone structure. Having the constituent unit (II) improves the adhesion of the photoresist film formed by the sensitive radiation linear tree to the substrate. Wherein, the lactone knot is calculated as an i-lactone ring having one ring (lactone ring) having an -oc(o)- structure as the first ring, and when only the lactone ring is present, it is called a single ring, In the case of other ring structures, the multi-ring constituent unit (II) is a structural unit represented by the following formula, regardless of the structure.艺佳为 , [A] ! alkyl base-i ring type (II composition of the group. Formula base. -23- 201232167 [Chemical 8 I Ru Rl1 Rl1 rLi

OCH3

(wherein, RL1 is a hydrogen atom, a methyl group or a trifluoromethyl group.) The single system which produces the structural unit (II) is represented by the following formula (L-1) -24-

S 201232167 【化9】

(L-1) virl3 (In the formula (L1), RL1 is a hydrogen atom, a methyl group or a trifluoromethyl group. RL2 is a single bond or a divalent linking group. RU is a monovalent organic group having a lactone structure.) RU The divalent linking group represented by the above is, for example, a linear or branched hydrocarbon group having a carbon number of 1 to 20 and a valence of 2 or 20.

The monovalent organic group having a lactone structure represented by Rt3 is, for example, a group represented by the following formula (L3-1) to (L3-6). [化1 0] * *

0 (L3-2)

(L3-3)

Ο L3-4)

Ο <y (L3-5)

Ο (In the formula (L3-1) to (L3-6), RLc1 is an oxygen atom or a methylene group. The rLc2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. rUe^O or 1. ～3的整-25- 201232167. * indicates a portion bonded to Rl2 in the above formula (L1), but the group represented by the formula (L3-1) to (L3-6) may have a substituent. The monomer to be used for the above-mentioned structural unit (II) is, for example, a monomer described in the paragraph [〇〇4 3] of International Publication No. WO 7/1 16664. [A] The content of the structural unit (Π) in the polymer is preferably 2 莫 mol% to 80 mol%, more preferably 30 mol% to 70 mol%. The [A] polymer may contain other structural units in addition to the structural unit (I) and the structural unit (II) within the range which does not impair the effects of the present invention. Other structural units include, for example, structural units having a polar group. <[A] Method for synthesizing polymer> [A] The polymer can be synthesized by a usual method such as radical polymerization. For example, a solution containing a monomer and a radical initiator is dropped into a solution containing a reaction solvent or a monomer to carry out a polymerization reaction; and a solution containing a monomer and a solution containing a radical initiator are separately dropped. a method of performing a polymerization reaction in a solution containing a reaction solvent or a monomer; and a solution containing a plurality of the respective monomers and a solution containing a radical initiator are separately dropped in a solution containing a reaction solvent or a monomer. It is preferred to carry out the synthesis by a method such as a method of carrying out a polymerization reaction. When the monomer solution is dropped and the reaction is carried out, the amount of the monomer in the monomer solution to be dropped is preferably 30 mol% or more, more preferably 50 mol%, based on the total amount of the monomers for polymerization. More than %, especially preferably 70% or more. The reaction temperature of these methods is appropriately determined by the starting agent species. Usually 30 ° C ~ 180 ° C, preferably 40 ° C ~ 160 ° C, more preferably

S -26- 201232167 5 0 ° C ~ 140 ° C. The dropping time varies depending on the reaction temperature, the kind of the initiator, the monomer to be reacted, and the like, and is usually 30 minutes to 8 hours, preferably 45 minutes to 6 hours, more preferably 1 hour to 5 hours. Further, the total reaction time including the dropping time is also the same as the dropping time, and is usually 30 minutes to 8 hours, preferably 45 minutes to 7 hours, more preferably 1 hour to 6 hours. The radical initiator for the above polymerization, for example, azobisisobutyronitrile (AIBN), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2, 2'-Azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and the like. These radical initiators may be used singly or in combination of two or more. The polymerization solvent is not particularly limited as long as it is a solvent (a nitrobenzene having a polymerization inhibitory effect or a thiol compound having a chain-moving effect). The solvent is not limited as long as it dissolves the solvent of the monomer. The polymerization solvent may, for example, be an alcohol solvent, a ketone solvent, a guanamine solvent, an ester solvent, a lactone solvent, a nitrile solvent or a mixed solvent thereof. These solvents may be used alone or in combination of two or more. The resin obtained by the polymerization is preferably recovered by a reprecipitation method. In other words, after the end of the polymerization reaction, the polymerization liquid is put into a reprecipitation solvent, and the intended resin is recovered in the form of a powder. The reprecipitation solvent may be used singly or in combination of two or more kinds of alcohols or alkanes. In addition to the sulphate method, the low molecular component such as a monomer or a low substance can be removed by a liquid separation operation, a column operation, a critical filtration operation, or the like, and the resin can be recovered. [A] The Mw of the polymer obtained by the GPC method is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably -27 to 201232167 3,000 to 30,000. [A] The Mw of the polymer is set within the above range, and the cross-sectional shape of the photoresist pattern is good. [A] The ratio of Mw to Mn of the polymer (Mw/Mn) is usually 1 to 3, preferably 1 to 2. . <[B]Acid Producer> [B] The acid generator generates an acid by exposure, and the acid dissociates the acid dissociable group present in the [A] polymer to generate a polar group such as a carboxyl group. As a result, the [A] polymer became poorly soluble for the developing solution. The form of the [B] acid generator in the composition may be in the form of a compound as described later (hereinafter sometimes referred to as "[B] acid generator"), or as a part of the polymer. The form to be included or these two forms. [B] An acid generator such as a key salt compound, a sulfonimide compound, a halogen-containing compound, a diazoketone compound or the like. Among these [B] acid generators, a key salt compound is preferred. The key salt compound is, for example, a phosphonium salt (containing a tetrahydrothiophene key salt), a phosphonium salt, a phosphonium salt, a diazo salt, a pyridyl salt or the like. The phosphonium salt is, for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium 2-bicyclo[2.2. 1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenyl camphorsulfonate, 4-cyclohexylphenyldiphenylphosphonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylphosphonium nonafluorobutane sulfonate, 4-cyclohexylphenyldiphenylphosphonium perfluorooctane sulfonate, 4-cyclohexylphenyldiphenylphosphonium 2 - Bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyl di

-28- S 201232167 phenyl camphorsulfonate, 4-methanesulfonylphenyldiphenylphosphonium trifluoromethane, 4-mercapto-diphenylphenyldiphenylphosphonium n-butane Sulfonate, 4-methane-propionic phenyldiphenylphosphonium perfluoro-n-octane sulfonate, 4-methanesulfonylphenyldiphenylphosphonium-2-bicyclo[2.2.1]heptan-2-yl -1,1,2,2-tetrafluoroethanesulfonate, 4-methylsulfonylphenyldiphenyl camphorsulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro- 6_(1-adamantanylcarbonyloxy)_hexane_丨·sulfonate, 2—adamantyl-1,1-difluoroethanesulfonate, and the like. In this case, triphenylsulfonium trisulfide compound, triphenylsulfonium nonafluorobutane sulfonate, 2-adamantyl-1,1-difluoroethane-1-sulfonate And triphenyl hydrazine, ^, plant tetrafluoro_6_ (1-golden carbonyloxy)-hexan-1-sulfonate is preferred. The tetrahydrothiophene key salt is, for example, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene iron trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrogen Thiophene nonafluoro-n-butane sulfonate, 1-(4. n-butoxynaphthalen-1-yl)tetrahydrothiophene-perfluoro- n-octane sulfonate, 1-(4-n-butoxynaphthalene- 1-yl)tetrahydrothiophene key 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1-(4-n-butoxynaphthalene-1 -yl)tetrahydrothiophene mothyl sulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophene trifluoromethanesulfonate, 1-(6-n-butoxynaphthalene-2 -yl)tetrahydrothiophene hexafluoro-n-butane sulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophene-perfluoro- n-octane sulfonate, 1-(6-n-butoxy 2-naphthyl-2-yl)tetrahydrothiophene key 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1-(6-n-butoxy Naphthalen-2-yl)tetrahydrothiophene mothyl sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene trifluoromethanesulfonate, 1-(3,5- Dimethyl-4-hydroxyphenyl)tetrahydrothiophene hexafluoro-n-butane sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene Fluorine-29- 201232167 n-octane sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydro 2-bicyclo[2.2.1]hept-2-yl-indole, ι,2 , 2-tetrafluoroethane sulfonate, 1 dimethyl-4-hydroxyphenyl)tetrahydrothiophene mothyl sulfonate, and the like. In the hydrogenthiophene key salt, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiafluoro-n-butane sulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrol Thiop-fluoro-n-octane sulfonate and 1-(3,5-dimethyl-4-hydroxyphenyl) tetra-gun nonafluoro-n-butane sulfonate are preferred. The iodide salt is, for example, diphenyl sulfonium trifluoromethanesulfonate, diphenyl n-butane sulfonate, diphenylphosphonium perfluorooctane sulfonate, diphenylbicyclo [2.2.1] hept-2- Base-1,1,2,2-tetrafluoroethanesulfonate, diphenyl sulfonate, bis(4.th-butylphenyl)-argon trifluoromethanesulfonic acid (4-tert-butyl Phenyl) fluorene nonafluorobutane sulfonate, bis(4-phenylphenyl)phosphonium perfluorooctane sulfonate, bis(4-tert-butylbenzene 2-bicyclo[2·2·1]g 2-yl-l,l,2,2-tetrafluoroethanesulfonate, ditributylphenyl)iodonium sulfonate, and the like. Among these samarium salts, bis-tributyl phenyl sulfonium hexafluoro-n-butyl sulfonate is preferred. The sulfonium imine compound is, for example, N-(trifluoromethanesulfonyloxy [2.2.1]hept-5-ene-2,3-dicarboxylimenide, N-(nonafluoro-n-butylalkyl)bicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxylimenine, N-(peralkylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy[2.2.1] g--5-discriminated-2,3-dicarboxy-branched Amine, N-(2-(3 [4.4.0.12'5·]7'1 G]dodecyl)-u • difluoroethanesulfonyloxy; ring [2.2.1]hept-5-ene- 2,3-dicarboxylimine imine, N-( camphortene sulfonate key-(3,5- these four-terminal nine-terminal hexa-hydrogen thiophene quinone hexafluoro-based fluorene- 2 fluorene barium salt) double third Butyl) hydrazine (4-(4-)bicyclic sulfonium oxyfluoride, N-( )bicyclotetracyclyl)bisdecyloxy-30-

S 201232167 ) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenine, and the like. Among these sulfonimide compounds, N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximine is preferred. These [B] acid generators may be used singly or in combination of two or more. [B] The amount of use of the acid generator in the case of an acid generator is usually 0.1 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the [A] polymer from the viewpoint of ensuring sensitivity and developability as a photoresist. It is preferably 0.5 parts by mass or more and 15 parts by mass or less. The amount of use of the [B] acid generator is in the above specific range, and a sufficiently satisfactory sensitivity can be obtained. <[C] Acid Diffusion Control Body> [C] The acid diffusion control system suppresses the diffusion phenomenon by diffusion of the acid generated by the [B] acid generator into the photoresist film, and has the effect of suppressing the photoresist film. The effect of a poor chemical reaction in the exposed region is not particularly limited as long as it has a polar group in the structure. The sensitive radiation linear resin composition for forming the pattern contains a [C] acid diffusion control body having a polar group, and thus the effect of addition of a usual acid diffusion control body is added. The roughness of the upper surface of the pattern of the resulting photoresist film can be suppressed. Further, in the groove pattern, the reverse cone shape can be suppressed, and in the hole pattern, the missing contact hole can be suppressed. The form of the composition of the acid diffusion controlling body may be a form of a free compound, a form in which a part of the polymer is incorporated, or both. The acid diffusion controlling body may, for example, be an amine compound, a nitrogen-containing compound containing a guanamine compound, a urea compound or the like. Among these, a nitrogen-containing compound is preferred. Λ -31 - 201232167 [c] The acid diffusion controlling body is preferably the above formula (1). In the above formula (1), R1, R2 and R3 are each a linear or branched alkyl group or a cycloalkyl group having 3 to 20 carbon atoms. However, any two of R1 to R3 are bonded to each other, and a heterocyclic ring can be formed together with them. R1, R2, R3 or the above heterocyclic ring; ^ are substituted by a polar group. In the above formula (1), R1, R2 and R3 represent a chain or a branched alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a fluorenyl group and the like. Among these, a methyl group, an ethyl group, and an alkyl group represented by R1, R2, and R3 in the above formula (1), for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclooctyl group, and a ring are preferable. Octylmethyl and the like. In the above formula (1), two mutually bonded nitrogen atoms of R1 to R3 together form a hetero ring, and for example, a pyrazinazine ring, a quinoxaline ring, an anthracene ring, a pyrrolidine ring or a piper is preferably a pyridyl group. Alkane ring and piperidine ring. In the above formula (1), R1, H2 or R3 is preferably a group of "". The group system group represented by the above formula (2), the [C] acid diffusion control system of the present invention dissociates from the acid dissociable group into a basic amine group by the sensitive radiation linear resin composition of the present invention The effect of the light obtained. In the above formula (1), the group represented by R1 to R3 represents a nitrogen atom which is independently bonded to a carbon number of 1 to 10 or an alkoxycarbonyl group [a carbon number of at least 1 of a hydrogen atom is 1). a cyclodyl group having a carbon number of 3 to 20, a cyclohexylmethyl group of 10, butyl or hexylpropyl group, and a ring, a pyrazole ring, a 哒π ring, and the like. Wherein, the two formula (2) represents an acid-dissociating group which has an action of an acid, and has a polar group -32- which is improved by the lithographic properties of the resist film.

S 201232167 is, for example, a hydroxyl group, a carboxyl group, a cyano group, an amine group, a decylamino group or the like. Among these, a hydroxyl group or a carboxyl group is preferred. The number of polar groups of the [C] acid diffusion controlling body is one or more, and more preferably 1 to 3. In the above formula (2), R4, R5 and R6 each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 4 to 12 carbon atoms. However, R4 and R5 are bonded to each other to form a cycloalkylene group having 4 to 12 carbon atoms together with the carbon atoms to which they are bonded. * indicates a site bonded to a nitrogen atom. In the above formula (2), the linear or branched alkyl group having 1 to 4 carbon atoms represented by R4, R5 and R6 may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group. Among these, a methyl group and an ethyl group are preferred. In the above formula (2), the monovalent alicyclic hydrocarbon group having 4 to 12 carbon atoms represented by R4, R5 and R6, and R4 and R5 are bonded to each other to form a carbon number 4 with the carbon atoms to which they are bonded. An alicyclic hydrocarbon group of -12, such as a cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cyclooctyl group, and a sulfhydryl group, a tricyclodecyl group, a tetracyclododecyl group, an adamantane group, and the like. The group has a group of a bridged alicyclic group. The group represented by the above formula (2) is, for example, represented by the following formula. -33- 201232167 [Chemical 1 1 * . Person "0 Λ Λ » ο person) C person H3C - D (2-1) (2-2) (2-3) (2-4) (2 -5) 〇丄〇 ♦ ο person. Everyone ολ H3C-^^ HaCO c2h5-^~^| Η, (2-7) (2-8) (2-9) (2-10) (2-11) 〇丄〇Λ人Ο h3c—ch3 (2-13) (2-14) (2-15) Small (2-16) Less (2-17) (2-18) ~b (2-β) C2Hs

(2-12)

A 丄 丄 Among these, (2-16) and (2-17) are preferred. The [C] acid diffusion control system containing a group having an acid dissociable group represented by the above formula (2), by the action of an acid, dissociates the acid dissociable group into a basic amine group, and has an improvement by the graph The effect of the lithographic properties of the photoresist obtained by the sensitive radiation linear resin composition in the type forming method. At this time, the carbon number of the dissociation group of the above acid-dissociable group is increased, and the dissociation energy of the dissociation group is improved, and the control of the alkalinity in the photoresist film is facilitated. Further, the evapotranspiration of the [C] acid diffusion control body of the photoresist film at the time of PB before exposure or after post-exposure baking after exposure can be suppressed, and the lithography performance can be further improved. The carbon number of the dissociation group is preferably from 4 to 20, more preferably from 4 to 13. When a hydrocarbon group having a carbon number of 4 or more is easily dissociated by an acid. The [C] acid diffusion control body is preferably represented by the following formula.

S -34- 201232167 【化1 2】

OH

(C-4) These acid diffusion control bodies may be used alone or in combination of two or more. The content of the [C] acid diffusion controlling agent is preferably 15 parts by mass or less, more preferably 0.001 to 10 parts by mass, even more preferably 0.005 to 5 parts by mass, per 100 parts by mass of the [A] polymer. When the content of the acid diffusion controlling agent is less than 0.001 part by mass, the pattern shape tends to be deteriorated, and when it exceeds 15 parts by mass, the sensitivity as a photoresist tends to be lowered. <Other components> The above-mentioned radiation-sensitive linear resin composition may contain a polymer having a fluorine atom (hereinafter also referred to as "[D] polymerization) which is added as necessary within a range which does not affect the effects of the present invention. The ")" and [E] solvents and other optional components are interfacially active oxime, alicyclic skeleton-containing compounds and sensitizers. The ingredients are detailed below. -35- 201232167 ([D] polymer) [D] Polymer is a fluorine atom-containing polymer. The pattern-forming sensitizing radiation linear resin composition contains a [D] polymer, which improves the hydrophobicity of the photoresist film and is excellent in substance elution inhibition during liquid immersion exposure. Since the resistive film and the liquid immersion liquid can be sufficiently increased in back contact angle, and there is no effect of leaving water droplets or the like during high-speed scanning exposure, the usefulness for liquid immersion exposure is high. The [D] polymer of the present invention is formed by polymerizing one or more monomers containing fluorine in the structure to form a monomer containing fluorine in the structure, for example, a fluorine atom in the main chain and a side chain. Fluorine atoms, main chain and side chains contain fluorine atoms. a monomer having a fluorine atom in the main chain, for example, an α-fluoroacrylate compound, an α-trifluoromethyl acrylate vinegar compound, a β-acrolein compound, a 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 a fluorine atom or a trifluoromethyl group or the like. The monomer having a fluorine atom in the side chain, for example, a side chain in which an alicyclic hydrocarbon compound of a norbornene is a fluorine atom 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 compound, the side chain of one or more olefins (the site containing no double bond), or the like, a fluorine atom or a fluoroalkyl group or a derivative thereof. a monomer having a fluorine atom in the main chain and the side chain, for example, α-fluoroacrylic acid, β-fluoroacrylic acid, α,β-fluoroacrylic acid, α-trifluoromethylacrylic acid, β-trifluoromethylacrylic acid, α, --trifluoromethacrylic acid, etc. with fluoroalkyl or its derivative

S-36-201232167 A compound of a biological ester, a side chain of a compound in which one or more hydrogens of a vinyl group is substituted with a fluorine or a trifluoromethyl group, is substituted by a fluorine or a fluoroalkyl group or a derivative thereof, and more than one bond The hydrogen on the double bond of the alicyclic olefin compound is substituted with 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 [D] polymer is not particularly limited, and the structural unit (III) represented by the following formula (5) is preferably used as the structural unit to which fluorine is imparted. 【化1 3】

A (5) (In the formula (5), R8 is hydrogen, a fluorine atom, a methyl group or a trifluoromethyl group. A is a linking group, and R9 is a linear chain having 1 to 6 carbon atoms containing at least one or more fluorine atoms. Or a branched alkyl group, or an alicyclic hydrocarbon group having 4 to 20 carbon atoms containing at least one fluorine atom or a derivative thereof.) The linking group represented by the above formula (5), A, for example, a single bond, An oxygen atom, a sulfur atom, a carbonyloxy group, an oxycarbonyl group, a decylamino group, a sulfonylamino group, a urethane group, or the like. The monomer of the structural unit (III) is provided, for example, trifluoromethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)f, ( Perfluoro- n-propyl methacrylate, perfluoroisopropyl (meth) acrylate, perfluoro-n-butyl (meth) acrylate, (permethyl-37-201232167) perfluoroisobutyl acrylate, (methyl) ) perfluorotributyl butyl acrylate, 2-(1,1,1,3,3,3-hexafluoropropyl) (meth) acrylate, 1-(2,2,3, (meth) acrylate 3,4,4,5,5-octafluoropentyl)ester, perfluorocyclohexylmethyl (meth)acrylate, 1-(2,2,3,3,3-pentafluoropropyl (meth)acrylate Ester), (meth)acrylic acid 1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,1〇, 10,10-heptadecane Mercapto) ester, 1-(5-trifluoromethyl-3,3,4,4,5,6,6,6-octafluorohexyl) (meth)acrylate, and the like. The [D] polymer may contain only one type or two or more types of structural units (III). [D] The content of the structural unit (III) in the polymer is preferably 10 mol% or more and 80 mol% or less when all the structural units in the [D] polymer are regarded as 100 mol%, more preferably The best is 20% or more and 50% or less. When the content of the structural unit (III) is less than 1% by mole, the contact angle may not be 70 degrees or more, and the dissolution of the acid generator such as the photoresist film may not be suppressed. [D] The polymer may contain, in addition to the above structural unit (III), one or more structural units having an acid dissociable group, for example, for controlling the dissolution rate of the developing solution, having a lactone skeleton or a hydroxyl group or a carboxyl group. The structural unit of the alicyclic compound has a structural unit of an alicyclic compound, and is a "other structural unit" derived from a structural unit of an aromatic compound in order to suppress light scattering caused by reflection of the substrate. With respect to the structural unit having the above acid-dissociable group, the structural unit of the [A] polymer can be used (description of 〇. The structural unit containing the above lactone skeleton can be used as the structural unit of the [A] polymer (II) -38-

S 201232167 The structural unit of the above alicyclic compound, for example, has a structural unit (IV) represented by the following formula (6). [化1 4] R10

ο — Β (In the formula (6), R1Q represents a hydrogen atom, a methyl group or a trifluoromethyl group. B is an alicyclic hydrocarbon group having 4 to 20 carbon atoms.) The carbon number represented by B of the above formula (6) is 4 The alicyclic hydrocarbon group of ~20, for example, derived from, for example, cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] Geng, bicyclo [2.2.2] octane, tricyclo [5.2.1.02, 6] a hydrocarbon group composed of an alicyclic ring of a cycloalkane such as a decane or a tetracyclo[6.2.1.13,6.〇2'7]dodecane or a tricyclo[3.3.1.1'7]decane. Some or all of one of the hydrogen atoms derived from the cycloaliphatic alicyclic ring may be substituted with a substituent. The substituent includes, for example, a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a cyano group, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group, and oxygen. The monomer of the above structural unit (IV) is provided, 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[5.2.1.〇2,6]癸-7-yl ester, (meth)acrylic acid-tetracyclo[6_2.1.13'6.〇2,7]12 Alkyl-9-yl ester, (meth)acrylic acid-tricyclo[3.3.1.13'7]non-1-yl ester, (meth)acrylic acid-tricyclo[3.3.1.13,7]non-2-yl ester Wait. Further, a monomer derived from the structural unit (V) of the above aromatic compound, -39-201232167, is provided, for example, styrene-butadiene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 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-methylstyrene , 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·t-butoxy-α-methylstyrene , 4-(2-ethyl-2-propoxy)styrene, 4-(2-ethyl-2-propoxy)-α-methylstyrene, 4-(1-ethoxyethoxy) Styrene' 4'(1_ethoxyethoxy)-α-methylstyrene, phenyl (meth)acrylate, benzyl (meth)acrylate, terpene '5-hydroxydecene, 1- Vinyl naphthalene, 2-vinyl naphthalene, 2-hydroxy-6-vinylnaphthalene, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, 1-naphthalene (meth)acrylate Methyl ester, decyl (meth) acrylate, 2- decyl (meth) acrylate, 9- decyl (meth) acrylate, 9- decyl methyl (meth) acrylate, 1-vinyl Inclusion of dinaphthalene and the like. The [D] polymer of the present invention may contain only one type or two or more kinds of the other structural units (I), (II), (IV) or (V) described above. The content ratio of these structural units is such that when the total structural unit in the [D] polymer is 1 〇〇 mol%, it is usually 〇 mol% or more and 80 mol% or less, preferably 〇 mol% or more. Moer% or less is more preferably 〇 mol% or more and 70 mol% or less. [D] The amount of the polymer to be used is 1 part by mass based on the [Α] polymer, and -40 to 201232167 is preferably 15 parts by mass or less, more preferably 2 parts by mass or more, of ι by mass or less. . The proportion of the fluorine atom in the [D] polymer is preferably larger than that of the [A] polymer. When the ratio of the fluorine atom in the polymer [D] is 100% by mass, the amount is usually 5% by mass or more, preferably 5% by mass to 50% by mass, more preferably 5% by mass. ~ 4 5 mass%. The content ratio of this fluorine atom can be determined by 13C-NMR. When the ratio of the fluorine atom in the polymer is larger than that of the [D] polymer, the photoresist film formed by the linear radiation resin composition containing the [D] polymer and the [A] polymer can be improved. The water repellency of the surface does not require the formation of an additional film during immersion exposure. In order to fully exert the above effects, the difference between the content ratio of the fluorine atom in the above [A] polymer and the fluorine atom in the above [D] polymer is preferably! More than or equal to 5% by mass, more preferably 5% by mass or more. <Delution method of [D] polymer> [D] polymer, for example, a monomer corresponding to each structural unit to be determined, which is polymerized in a suitable solvent using a radical polymerization initiator, and the above [A] The synthesis method of the polymer is produced in the same manner. [D] The weight average molecular weight (Mw) of the polymer measured by a gel permeation chromatography (GPC) method, preferably 1, 〇〇〇~5 〇, 〇〇〇, more preferably For 1, 〇〇〇~3〇, 〇〇〇, especially good for 1, 〇〇〇~1〇, 〇〇〇. When the Mw of the polymer [A] is less than 1,000, a sufficient previous contact angle cannot be obtained. Further, when Mw exceeds 50,000, the developability as a photoresist tends to be lowered. -41 - 201232167 The ratio (Mw/Mn) of the Mw of the polymer to the number average molecular weight (??) in terms of polystyrene measured by the GPC method is usually from 1 to 3, preferably from 1 to 2. ([E] Solvent) This composition usually contains a solvent. The solvent is not particularly limited as long as it dissolves at least the above [A] polymer, [B] acid generator, [C] acid diffusion controller, and, if necessary, the [D] polymer and other optional components. . The solvent may, for example, be an alcohol solvent, an ether solvent, a ketone solvent, a guanamine solvent, an ester solvent or a mixed solvent thereof. Specific examples of the solvent are the same as those exemplified in the pattern forming step (3). Among these, propylene glycol monomethyl ether, cyclohexanone and γ-butyrolactone are preferred. These solvents may be used singly or in combination of two or more. <Other optional components> The composition may contain various additives in order to adjust or enhance the patterning characteristics or the processing characteristics of the substrate. (Interfacial activity 剤) The surfactant has an effect of improving coatability, streaking property, developing property and the like. (compound containing alicyclic skeleton)

S-42 - 201232167 The compound containing an alicyclic skeleton has an effect of improving dry etching resistance, pattern shape, adhesion to a substrate, and the like. (Sensitizer) The sensitizer is an effect of increasing the amount of [B] acid generator produced, and has an effect of improving the "apparent sensitivity" of the composition. <Preparation of Sensitive Radiation Linear Resin Composition> The composition can be added, for example, by [A] polymer, [B] acid generator, [C] acid diffusion control body, if necessary in an organic solvent. The [D] polymer and other components are mixed at a predetermined ratio to prepare. Further, the composition can be used in a state of being dissolved or dispersed in a suitable organic solvent. [Embodiment] [Examples] Hereinafter, the present invention will be more specifically illustrated by the examples, but the present invention is not limited to the examples. The weight average molecular weight (Mw) and the number average molecular weight (??) were determined by the following conditions using a GPC column (TOSOH, G2000HXL 2, G3000HXL 1 , G4000HXL 1).

Column temperature: 40 ° C Solvent: tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) Flow rate: 1.0 m L / min -43 - 201232167 Sample concentration: 1.0% by mass Sample injection amount: ΙΟΟμί Detector: Differential refractometer standard substance: The monodisperse polystyrene 'H-NMR analysis and 13 C-NMR analysis were measured using a nuclear magnetic resonance apparatus (Sakamoto Electronics Co., Ltd., JNM-EX270). Synthesis of Polymer > [A] The monomer for the synthesis of the polymer is represented by the following formula. [化1 5]

(M-1) Ο (M-2) (M-3)

(M-4) (M-5) [Synthesis Example 1] : Synthesis of (A-1) 9 g (50 mol%) and formula °) were dissolved in 60 g of 2-butanone to prepare a solution. Next, a monomer represented by the following formula (M-1), which is represented by the monomer 12 (M-2), 17.18 (50 mol% Å) is injected into 2,2'-azobisisobutyronitrile 〇.5〇.

S-44-201232167 A 3-neck flask of 30 keol of 2-butanone was purged with nitrogen for 30 minutes, then heated to 80 ° C while stirring the reaction vessel, and pre-prepared by dropwise addition using a dropping funnel for 3 hours. Monomer solution. 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 ° C or lower by water cooling. The mixture was poured into 600 g of methanol, and the precipitated white powder was obtained by filtration. The white powder obtained by filtration was washed with 120 g of methanol in the slurry state, and then again filtered, and dried at 50 ° C for 12 hours to obtain a white powder polymer (Al) (Mw = 3,000). , Mw / Mn = 1.56 'yield = 82%). The ratio of the structural unit derived from (M-l) / (M-2) in (A-1) is 49/51 (% by mole). [Synthesis Examples 2 to 4] Polymers (A-2) to (A-4) were obtained in the same manner as in Synthesis Example 1 except that the monomers of the type and amount of Table 1 were used. Further, the content ratio, Mw, Mw/Mn ratio and yield (%) of each structural unit of each of the obtained polymers are shown in Table 1. I, Table 1] Synthesis Example 1 Synthesis Example 3 Synthesis Example 4 [A] Polymer compounding amount Content ratio of each structural unit (% by mole) Yield (%) Physical properties 値ί- 1/Μ- 2 Μ- 2/ M- 3 M— 1/M—2/M- 4 Μ- 2/M—VM- 5 50/50 50/50 40/50/10 50/40/10

Mw/Mr 49.0/51.0 49.5/50.5 39.5/50.0/10.5 82 72 13,000 T,200 7,500 1.56ΤδΓ 1.61 Synthesis of polymer> [D] The monomer for the synthesis of the polymer is represented by the following formula. 201232167 【化1 6】 Λτ°ο

ο

CF (Μ-6)

(Μ-7)

[Synthesis Example 5]: Synthesis of (D-1) The monomer represented by the following formula (Μ-6) 35 8g (7〇m〇p/e) and the monomer i4 represented by the formula (M-7). 2 g (30 m〇l%) was dissolved in 2 丁 of 5 -butanone, followed by injection of 5.17 g of 2,2'-azobisisobutyronitrile. Next, a 500 mL three-necked flask of 5 〇g of 2-butanone was injected and purged with nitrogen for 3 minutes, and then heated to 80 ° C while stirring the reaction pot, and the pre-modulated monomer was added dropwise over 3 hours using a dropping funnel. Solution. The polymerization reaction was carried out for 6 hours starting from the start of the dropwise addition as the polymerization start time. After the completion of the polymerization, the solution was cooled to 3 〇 〇c with water cooling, and the reaction solution was transferred to a 2 L separatory funnel, and then the polymerization solution was uniformly diluted with 150 g of hexane, and 600 g of methanol was introduced and mixed. Then, 30 g of distilled water was poured and stirred for 30 minutes. Then, the lower layer was recovered to form a propylene glycol monomethyl ether acetate solution. The polymer (D-l) is thus obtained (Mw = 7,000,

Mw / Mn = 1.60' yield = 66%). The ratio of structural units derived from (Μ-6)/(Μ·7) in (D-1) is 71/29 (mol%). -46 -

S 201232167 [Synthesis Example 6] A polymer (D-2) was obtained in the same manner as in Synthesis Example 5 except that the monomer of the type and amount of Table 2 was used. Further, the content of the structural unit of the obtained polymer, the ratio of Mw, Mw/Mn, the yield (°/〇), and the content of the low molecular weight component are shown in Table 2. [Table 2] [D] Mixing compound amount of indifference %) Each knotted Nylon containing Meng Haner%) Yield (%) Physical surface blending amount Mw Mw/Mn Synthesis example 5 D- 1 Μ- 6/ M- 7 70/30 71.0/29.0 66 7,000 1.6 Synthesis Example 6 D-2 Μ — 8/M— 9 20/80 20.5/79.5 68 7,200 1.51 The [B] acid used for the preparation of the sensitive radiation linear resin composition The product, the [C] acid diffusion inhibitor and the [E] solvent are as follows. <[B]Acid Producer> B-1: Triphenylsulfonium 1,1,2,2-tetrafluoro-6-(1-adamantanecarbonyloxy)-hexane-1 represented by the following formula -sulfonate B-2: triphenylsulfonium 2-adamantyl-1,1-difluoroethanesulfonate-47-201232167 represented by the following formula

,〇,^^^C,so3-

V st like &, S03- <Β_2) <[C] acid diffusion control body> C-1 to C-6: a compound represented by the following formula

&lt;[E]solvent&gt; E-1: propylene glycol monomethyl ether acetate-48 201232167 E-2: cyclohexanone E-3: γ·butyrolactone &lt;modulation of sensitive radiation-sensitive resin composition&gt; [Example 1] 100 parts by mass of a polymer (Α-1), an acid generator (Β-1) 12.8 parts by mass, an acid diffusion controlling body (Cl) I·7 parts by mass, and a polymer (D-1) 3 The mass fraction and the solvent (E-1) 2,185 parts by mass, (E·2) 935 parts by mass, and (Ε-3) 30 parts by mass were mixed and modulating the radiation-sensitive linear resin composition (R-1). [Examples 2 to 9 and Comparative Examples 1 to 2] In addition to the types and amounts of [Α] polymers, [Β] acid generators, [C] acid diffusion controllers, and [D] polymers described in Table 3 were used. Further, the radiation sensitive linear resin compositions (R-2) to (R-1 1 ) were prepared in the same manner as in Example 1. [Table 3] Sensitive radiation linear resin composition [A] Polymer [Β] Acid generator [C] Acid diffusion control body [D] Polymer [E] Solvent mm Mass parts mm Mass parts Lion substance part quality S Mm parts by weight Example 1 R-1 A- 1 100 Β-1 12.8 Cl 1.7 D- 1 3 E_l/E-2/E-3 2.185/935/30 Example 2 R-2 Α-1 100 Β- 1 12.8 C-2 1.2 D— 1 3 E- 1/E- 2/E- 3 2.185/935/30 «Example 3 R- 3 Α-1 100 Β-1 12.8 C-3 1.9 D-1 3 E - 1/E-2/E- Ξ 2.185/935/30 «Example 4 R-4 Α-1 100 Β-1 12.8 C-4 1.3 D-1 3 E- 1/E- 2/E- 3 2.185 /935/30 Official Example 5 R-5 A-2 100 Β-1 12.8 C-4 1.3 D-1 3 E-1/E-2/E-3 2.185/935/30 Example 6 R-6 A -3 100 Β-1 12.8 C-4 1.3 D-1 3 E-1/E-2/E-3 2.185X935/30 苜 Example 7 R-7 A-4 100 Β-1 12.8 C-4 1.3 D -1 3 E-1/E-2/E-3 2.185/935/30 Example 8 R-8 Α-1 100 Β-2 10.5 C-4 1.3 D- 1 3 E- 1/E-2/E -3 2.185/935/30 Official Example 9 R-9 Α-1 100 Β-1 12.8 C-4 1.3 D-2 3 E- 1/E-2/Ea 2.185/935/30 Comparative Example 1 R-10 Α-1 100 Β-1 12.8 C-5 1.4 D-1 3 El/EZ/E-3 2.185/935/30 Specific hinge example 2 R- 11 A- X 100 Β-1 12.8 C-6 2.8 D-1 3 E-1/E-2 /E-3 2.185/935/30 &lt;Formation of photoresist pattern&gt; [Example 10] An organic antireflection film forming agent (Nissan Chemical Co., Ltd., ARC66) was coated on the surface of the wafer to form an organic reflection having a film thickness of 105 nm. Prevent film. -49- 201232167 of this substrate was coated with a CLEAR TRACK (Tokyo Electronics Co., Ltd., ACT12) spin-sensitive radiation linear resin composition (R-1), and pre-baked on a hot plate at 90 ° C for 60 seconds to form a film. A 0.1 Ομιη photoresist film is used. The liquid immersion liquid uses pure water. This photoresist film uses a full-area reduction projection exposure device (NIKON, S610C, opening number 1.30, illumination Quadrupole), and a dot pattern mask. The photoresist film was immersed in water, and the projection exposure was reduced. Then, after exposure and baking at 100 ° C for 60 seconds, the film was imaged by butyl acetate at 23 ° C for 30 seconds to 4-A. After the solvent treatment of the keto-pentanol solvent for 10 seconds, the wafer was spun at 2,000 rpm for 10 seconds to dry to form a negative resist pattern. [Examples 1 to 28 and Comparative Examples 3 to 6] A photoresist pattern was formed in the same manner as in Example 1 except that the sensitive radiation linear resin composition and the developer liquid of the type described in Table 4 were used. <Evaluation> Regarding the formation of each photoresist pattern, the next step was performed. The evaluation results are shown in Table 4. [Roughness of Resistive Surface (nm)] Roughness of Resistive Surface The measurement was performed using an atomic force microscope (0.1 0〇x〇. 1 ΟΟμπι). After measuring the roughness of the photoresist surface, the RMS calculated by RMS was judged to be "good" when it was less than 10 nm, and when it was 10 nm or more. It is judged as "bad". -50-

S 201232167 [Sensitivity (mJ/cm2)] The diameter of the hole pattern after the reduction projection exposure is 0.05 5 μm, and the pitch is Ο.ΙΙΟμιη, and the reticle with the dot pattern is immersed in water to expose it. The hole pattern is an exposure amount when the diameter is 〇55 μmη and the pitch is 0.1 ΙΟμηη as the optimum exposure amount, and the optimum exposure amount is used as the sensitivity (mJ/cm 2 ). Also, the length measuring system uses a scanning electron microscope (Hitachi Bureau of Technology, CG4000). [Resolving property (nm)] The aperture of the hole pattern after the projection exposure is reduced to 0.05 μm, and the pitch is Ο.ΠΟμπι with a dot pattern type reticle. When the exposure amount is increased by liquid immersion, the obtained hole is measured. The smallest size of the pattern. When the minimum contact size disappears and the minimum size of the hole is less than 55 nm, it is judged as "good". When the contact hole disappears or the minimum size of the hole is 55 nm or more, it is judged as "poor". [Graph Size Uniformity (CDU) Using a length measuring SEM (Scanning Electron Microscope) (Hitachi High-Tech Co., Ltd. 'CG4 00 0), a pore pattern of 0.05 5 μm of the photoresist film formed on the substrate was observed from the upper portion of the pattern at the optimum exposure amount. The diameter was measured at an arbitrary point, and the measurement deviation was evaluated as 3σ. When it was less than or equal to 4 μm, it was judged as "good", and when it was more than 〇.〇〇4 μιη, it was judged as "poor". [Sectional shape] Observed the shape of the hole pattern of 0.055μιη in the above sensitivity evaluation 201232167 (Hitachi High-Tech Co., Ltd., S-48 00), and measured the rectangular shape and the line width in the middle of the photoresist pattern. When the line width La of Lb and the upper portion of the film is within the range of 0.9S (La/Lb) S1.1, it is judged as "good", and when it is outside the above range, it is judged as "poor". [Table 4] Sensitive radiation linear resin composition Development liquid surface roughness sensitivity (mJ/cm2) Resolution (rnn) Pattern size uniformity section shape Example 10 R-1 Butyl acetate good 19.0 47.5 Good good example 11 R-1 Isoamyl acetate good 20.0 47.1 Good good 贲 Example 12 R-1 Methyl ethyl ketone good 23.0 46.5 Good good Example 13 R-2 Butyl acetate good 18.0 51.5 Good good example 14 R-2 Methyl ethyl ketone good 22.5 50.8 good good example 15 R-3 isoamyl acetate good 17.5 46.9 good good example 16 R-3 methyl amyl ketone good 23.0 46.2 good good example 17 R-4 butyl acetate Good 18.0 49.5 Good good Example 18 R-4 Methyl amyl ketone good 22.5 49.1 Good good Example 19 R-5 Butyl acetate good 16.5 49.3 Good good Example 20 R-5 Methyl amyl ketone good 20.0 48.9 Good Good Practice Example 21 R-6 Butyl Acetate Good 18.0 49.9 Good Good Practice 22 R-6 Methyl amyl ketone Good 22.5 49.1 Good Good 寅 Example 23 R-7 Butyl Acetate Good 18.5 48.9 Good, Example 24 R-7 Methyl amyl ketone good 22.5 48.8 Good good Example 25 R-8 Butyl acetate good 19.0 48.8 Good good Example 26 R-8 Methyl amyl ketone good 23.0 48.7 Good good practice Example 27 R-9 Butyl Acetate Good 19.0 51.5 Good Good Example 28 R-9 Methyl amyl ketone good 23.5 50.5 Good good Comparative Example 3 R-10 Bad butyl acetate 18.5 57.5 Poor defect Comparative Example 4 R-10 A Pentylpyridinium 23.0 57.1 Adverse defect Comparative Example 5 R-11 Butyl acetate defect 19.0 58.4 Adverse defect Comparative Example 6 R-11 Methyl amyl ketone defect 22.5 58.1 Adverse defects As can be seen from Table 4, the pattern of the present invention The photoresist pattern formed by the formation method is excellent in cross-sectional shape, pattern size uniformity, and resolution. Compared with the comparative example, the roughness of the upper surface of the pattern can be more suppressed. [Industrial Applicability] According to the present invention, in the lithography step, the roughness of the upper surface of the pattern of the photoresist film can be suppressed, and excellent resolution, pattern size uniformity, and cross-sectional shape can be formed. Graphic type. This makes it possible to use various electronic device configurations such as semiconductor devices and liquid crystal devices that require further miniaturization. -52-

S

Claims (1)

201232167 VII. Patent application scope: 1 · A method for forming a pattern, which includes the following method of forming a groove pattern and/or a hole pattern: (1) a sensitive radiation linear resin a step of forming a photoresist film on the substrate; (2) an exposure step of exposing the photoresist film; and (3) developing the exposed photoresist film by a developing solution The developing step is characterized in that the developing solution contains 80% by mass or more of an organic solvent, and the sensitive radiation linear resin composition contains: [A] having a structural unit containing an acid-dissociable group, and is caused by an action of an acid An increased polarity polymer, [B] a sensitive radiation linear acid generator, and [C] an acid diffusion control body having a polar group. 2. The method for forming a pattern according to item 1 of the patent application, wherein the [C] acid diffusion control body is a nitrogen-containing compound represented by the following formula (1), [Chemical Formula 1] R1 i (" R〆 (Formula ( In 1), R1, R2 and R3 are each independently a linear or branched alkyl group having a carbon number of 1 to ίο, a cycloalkyl group having a carbon number of 3 to 20, or an alkoxycarbonyl group, but R1 to R3. Two mutually bonded 'may form a heterocyclic ring together with the nitrogen atom to which they are bonded, and at least one of R1, R2, R3 or a hydrogen atom of the above heterocyclic ring is substituted by a polar group.) -53- 201232167 3. Application The method for forming the pattern of the first or second aspect of the patent range wherein the polar group is a hydroxyl group or a carboxyl group. 4. The method for forming a pattern according to the second or third aspect of the patent application' wherein the above R1, R2 and R3 are used. One group represented by the following formula (2) 'Chemical 2' (2) R4--R6 R5 (In the formula (2), R4, R5 and R6 are each independently a linear chain having a carbon number of 1 to 4. Or a branched alkyl group or a cycloalkyl group having 4 to 12 carbon atoms, but R4 and R5 are bonded to each other to form a cycloalkylene group having a carbon number of 4 to 12 together with the carbon atoms to which they are bonded, * Nitrogen The method of forming a pattern according to any one of the above claims, wherein the acid dissociable group of the [A] polymer has an alicyclic group. The method for forming a pattern according to any one of items 1 to 5, wherein in the (2) exposure step, the plurality of exposures are performed. 7. The sensitive radiation linear resin composition contains the following (1)~ (3) a sensitive radiation linear resin composition for forming a groove pattern and/or a hole pattern, and (1) a step of forming a photoresist film by applying a radiation sensitive linear resin composition onto the substrate; (2) an exposure step of exposing the photoresist film; and (3) a developing step of developing the exposed photoresist film by a developing solution; S-54-201232167 characterized by the above-mentioned display The liquid electrolyte contains 80% by mass or more of an organic solvent, and the above-mentioned radiation-sensitive linear resin composition contains: [A] a polymer having a structural unit containing an acid-dissociable group and having an increased polarity by an action of an acid, [B] Sensitive radiation linear acid generator and [C] acid extension with polar groups -55- 201232167 IV. Designation of the representative figure: (1) The representative figure of the case is: No (2) The symbol of the symbol of the representative figure is simple: No 201232167 If there is a chemical formula in the case, please reveal the best invention Chemical formula of the feature: none