TW201229067A - Pattern forming method and radiation-sensitive resin composition - Google Patents

Abstract

The purpose of the present invention is to provide a pattern forming method that has excellent lithographic properties such as CDU, and can suppress roughness in the surface of an exposed section after development, and a radiation-sensitive resin composition optimal for the pattern forming method. The present invention is a pattern forming method containing (1) a step for forming a resist film on a substrate using a radiation-sensitive resin composition, (2) an exposure step, and (3) a development step, the pattern forming method being characterized in that an organic solvent constitutes 80 mass% of the developing fluid in the development step, and in that the radiation-sensitive resin composition contains (A) a polymer in which a structural unit (I) represented by formula (1) constitutes 45-80 mol% thereof, and (B) a radiation-sensitive acid generator.

Description

201229067 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a pattern forming method and a radiation sensitive resin composition. [Prior Art] With the miniaturization of various electronic devices such as semiconductor devices and liquid crystal devices, the miniaturization of the photoresist pattern in the lithography step is also required. Representative short wavelength radiation is listed as an ArF excimer laser. Use these to form a fine photoresist pattern with a line width of about 9 Onm. Various photoresist compositions that can correspond to the short-wavelength radiation have been reviewed, and it is known that in the photoresist composition, an acid is generated in the exposed portion by irradiation (exposure) of radiation, by the acid The catalytic action causes the exposed portion and the unexposed portion to have a difference in solubility to the developing liquid, and a resistive linear thermoplastic resin composition of the resist pattern is formed on the substrate. On the other hand, a technique utilizing the characteristics of the sensitive radiation linear resin composition and using an existing device to increase the resolution without increasing the number of steps is known to use an organic solvent having a lower polarity than the alkaline aqueous solution in the developing solution ( Refer to JP-A-2000-199953). This is because when a groove pattern or a hole pattern is formed using an alkaline aqueous solution in a developing 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 fineness can be formed. Graphic type. However, in the method of forming the above-mentioned photoresist pattern using an organic solvent in a developing liquid, when the linear photosensitive resin composition of the past sensitive radiation is used, the roughness of the exposed surface after development is quite large, and currently, it is not completely Meets the lithography characteristics of -5 - 201229067 LWR (line width roughness), CDU (critical dimension uniformity). Accordingly, it is desirable to use the above-described pattern forming method of the organic solvent in the developing liquid and the most appropriate combination of the radiation sensitive linear resin composition. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2000-199953 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The present invention has been made based on the above problems, and an object of the present invention is to provide a suppression image. The surface roughness of the exposed portion, the pattern forming method excellent in lithographic characteristics such as CDU, and the sensitive radiation linear resin composition most suitable for the pattern forming method. [Means for Solving the Problems] The invention for solving the above problems is a pattern forming method comprising the pattern forming method of the following steps: (1) forming a photoresist film on a substrate by using a sensitive radiation linear resin composition. a step of (2) exposing the photoresist film, and (3) a step of developing the exposed photoresist film, wherein the method is characterized in that the developing solution in the developing step contains 8% by mass Organic solvent, and 201229067 The above-mentioned radiation sensitive linear resin composition contains [A] The structural unit (I) represented by the following formula (1) (hereinafter sometimes referred to as "structural unit (I)") is 45%. a polymer having an ear percentage of 8 〇 or less or less (hereinafter sometimes referred to as "[A] polymer"), and [B] a radiation-sensitive linear acid generator (hereinafter sometimes referred to as "[B] acid generator) "), [Chemical 1]

(In the formula (1), 'R1 is a hydrogen atom or a methyl group, and R2 is a monovalent acid-dissociable group, and is a linear or branched hydrocarbon group or an alicyclic group, and the hydrocarbon group or the alicyclic group may be The skeleton chain contains -0-, and some or all of the hydrogen atoms of the above alicyclic group may be substituted by a linear or branched hydrocarbon group having 1 to 4 carbon atoms, but the carbon number in R2 is 1~9). The pattern forming method of the present invention is characterized in that a developing liquid having a lower polar ratio than a basic aqueous solution commonly used in the formation of a positive chemically amplified photoresist as a developing liquid is used in the developing step, that is, it contains 80% by mass. The above-mentioned organic solvent imaging solution (a developing solution which can dissolve an unexposed portion in the photoresist film to form a negative image). The organic solvent is excellent in affinity with the surface of the above-mentioned resist film, and as a result, developability can be improved. Further, the sensitive radiation linear resin composition used in the pattern forming method contains the [A] polymer and the [B] acid generator, and the acid generated from the acid generator of 201229067 [B] by the above exposure step, The [A] polymer has a protective group which is an acid dissociable group. As a result, the polarity of the [A] polymer in the exposed portion is increased, so that the poor solubility of the lower polarity developing solution used in the present invention is increased, and the polymer in the photoresist film of the unexposed portion is promoted. Dissolve the imaging solution. On the other hand, when the conventional linear radiation resin composition is used, the above-mentioned protective group which has been detached remains in the photoresist film, and the surface of the exposed portion is defective due to dissolution of the developing solution. The sensitive radiation linear resin composition of the present invention is characterized in that a smaller protecting group having a carbon number of 1 to 9 (hereinafter sometimes referred to as "small protecting group") is selected as a protective group, and by the above structural unit (I) The content ratio is 45 mol% or more and 80 mol% or less, so that the [A] polymer contains a large number of small protecting groups. For this reason, the small protective group which is detached is evaporated by the post-exposure baking (heating step) after the exposure step, thereby lowering the roughness of the exposed portion surface. Further, by combining the pattern forming method containing the composition and characteristics of the [A] polymer having the above specific structure, it is possible to form a pattern excellent in lithographic properties such as CDU. The [A] polymer preferably further contains a structural unit having a lactone skeleton (11). By further including the structural unit (Π) of the [A] polymer, the basic characteristics of the photoresist such as the adhesion between the photoresist film and the substrate can be further improved. The polymer [A] preferably further contains a structural unit (III) represented by the following formula (2), and the content ratio of the structural unit is not more than 20% by mol%, 201229067 [Chemical 2] R3

(In the formula (2), R3 is a hydrogen atom or a methyl group, and R4 is a group having a monovalent alicyclic group having 10 to 20 carbon atoms, and some or all of the hydrogen atoms of the alicyclic group may pass through carbon Number 1~4 alkyl substitution). R4 in the above formula (2) is a one-valent alicyclic group having 10 to 20 carbon atoms, and is a large protecting group (hereinafter sometimes referred to as "large protecting group"). By including the structural unit having the large protecting group in the specific ratio described above, on the one hand, the roughness is lowered, and on the other hand, the etching resistance of the photoresist film can be improved. The sensitive radiation linear resin composition of the present invention is a sensitive radiation linear resin composition used in a pattern forming method comprising the following steps: (1) a step of forming a photoresist film on a substrate by using a radiation sensitive linear resin composition, ( 2) a step of exposing the photoresist film, and (3) a step of developing the exposed photoresist film, wherein the sensitive radiation linear resin composition is characterized by containing [A] represented by the following formula (丨) a polymer having a structural unit (I) content of 4 5 mol% or more and 80 mol% or less, and [B]minton ray acid generator, 201229067 [Chem. 3]

(In the formula (1), R1 is a hydrogen atom or a methyl group, and R2 is a monovalent acid-dissociable group, and is a linear or branched hydrocarbon group or an alicyclic group, and the hydrocarbon group or the alicyclic group may be The skeleton chain contains -0-, and some or all of the hydrogen atoms of the above alicyclic group may be substituted by a linear or branched hydrocarbon group having 1 to 4 carbon atoms, but the carbon number in R2 is 1~9). By using the sensitive radiation linear resin composition in the pattern forming method described above, the roughness can be reduced, and a photoresist pattern excellent in lithographic characteristics can be obtained. [Effect of the Invention] According to the present invention, it is possible to provide a pattern forming method capable of suppressing the roughness of the surface of the exposed portion after development, and having excellent lithographic characteristics such as CDU, and the most suitable method for forming the pattern. Radiation-Linear Resin Composition [Embodiment] <Formation Method of Pattern> The pattern forming method of the present invention comprises the steps of (1) forming a photoresist film on a substrate using a radiation-sensitive linear resin composition (hereinafter sometimes referred to as "(1)Step")' (2) The step of exposing the above-mentioned photoresist film (hereinafter referred to as "(2) step" in -10-201229067), and (3) making the exposed photoresist film visible A pattern forming method of a step (hereinafter sometimes referred to as "(3) step)), wherein the developing solution in the developing step contains 80% by mass or more of an organic solvent, and the sensitive radiation linear resin is composed of The material contains a [A] polymer and a [B] sensitive radiation linear acid generator. Each step is detailed below. [(1) Step] In this step, the sensitive radiation linear resin composition of the present invention is applied onto a substrate to form a photoresist film. As the substrate, a conventional substrate such as a wafer or an aluminum-coated wafer can be used. Further, an organic or inorganic antireflection film can be formed on the substrate as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. The coating method is exemplified by spin coating, wound coating, roll coating, and the like. Further, the film thickness of the formed photoresist film is usually 0.01 μm to 1 μm, preferably Ο.ΟΙμιη~0_5μιη. After coating the composition, the solvent in the coating film may be volatilized by pre-baking (ΡΒ) as needed. The heating condition of the crucible is suitably selected depending on the composition of the composition, but it is usually from about 30 ° C to about 200 ° C, preferably from 50 ° C to 150 ° C. In order to prevent the influence of the alkaline impurities and the like contained in the environmental atmosphere, a protective film disclosed in, for example, JP-A-5-88598 can be provided on the photoresist layer. In addition, in order to prevent the outflow of the acid generator or the like from the photoresist layer, a protective film for liquid immersion disclosed in, for example, JP-A-2005-35 523 84 may be provided on the photoresist layer. Again, these techniques can be employed. -11 - 201229067 [(2) Step] This step is to expose the mask by the specific pattern and the desired area of the photoresist film formed in the step (1) as needed. For example, a contour pattern can be formed by reducing the projection exposure through a cross-talk pattern mask. Also, perform more than two times with the desired pattern and mask pattern. When performing exposure, it is preferable to perform exposure continuously. In the case of multiple exposures, the first pass of the transmission line and the spacer pattern mask is performed on the area, and then the exposure portion of the first exposure is performed to cause the line to perform the second reduction projection exposure. The first exposure portion is preferably orthogonal to the first exposure portion. By orthogonality, a true circular contact hole pattern can be easily formed by the exposure portion. Further, the exposure liquid is exemplified by water or a fluorine-based inert liquid or the like. The liquid immersion liquid is transparent, and in order to maintain the deformation of the optical image projected on the film, it is preferred that the liquid having a refractive index as small as possible is outside the viewpoint that the exposure light source is ArF excimer laser light (wavelength 193 nm). In terms of ease of operation and ease of operation, When water is used, a small proportion of the additive which increases the interfacial activity when water is reduced may be added. Preferably, the additive dissolves in the photoresist layer and is for the optical coating beneath the lens. The water used is preferably distilled water. The radiation used in the exposure is selected according to the [B] acid generator selection. For example, the liquid immersion liquid such as ultraviolet rays, far ultraviolet rays, and X-rays may be exposed to the area where the projection is reduced. The method of projecting the exposure crossover is that the exposure wavelength used in the exposure portion is smaller than that in the unexposed portion, but in particular, in addition to the above-mentioned preferred use of the water surface tension, the type on the wafer is not negligible. , charged particles -12- 201229067 bundles and so on. The above is preferably a far ultraviolet ray represented by an ArF excimer laser or a KrF excimer laser (wavelength 248 nm), more preferably an ArF excimer laser. The exposure conditions such as the amount of exposure are appropriately selected depending on the composition of the composition, the type of the additive, and the like. In the pattern forming method of the present invention, there may be a plurality of exposure steps, the same light source may be used for the plurality of exposures, 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. The dissociation of the acid dissociable group in the composition can be carried out smoothly by performing PEB'. The heating condition of PEB is usually 30 ° C to 200 ° C, preferably 50 ° C to 170 ° C.

[(3) Step] This step is carried out by exposure after exposure in the step (2), and development is carried out using a negative-type developing solution containing 80% by mass or more of an organic solvent. The negative-type developing solution is a solution for selectively dissolving and removing the developing liquid of the low-exposure portion and the unexposed portion. The organic solvent contained in the negative-working liquid is preferably at least one selected from the group consisting of an alcohol solvent, an ether solvent, a ketone organic solvent, a guanamine solution, an ester organic solvent, and a hydrocarbon solvent. The alcohol solvent is exemplified by, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, n-pentanol, isoamyl alcohol, 2-methylbutyl Alcohol, second pentanol, third pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, second hexanol, 2-ethylbutanol, second heptanol, 3-glycol Alcohol, n-octanol, 2-ethylhexanol, second octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n--13-201229067 alcohol, second-undecyl alcohol , trimethyl decyl alcohol, second-tetradecanol, second heptadecyl alcohol, decyl alcohol, phenol, 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-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol 'tripropylene glycol 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 ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, ethyl positive Butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl fluorenone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentane A ketone solvent such as ketone, etidylacetone or acetophenone. The guanamine solvent is exemplified by, for example, N,N '-dimethylimidazolidinone, N-methylformamide 'N,N-dimethylformamide, N,N-diethylformamide, B.醯-14- 201229067 Amine, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, and the like. The ester solvent is exemplified by, for example, diethyl carbonate, propyl 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 hexyl ester, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-decyl acetate, methyl acetoxyacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, acetic acid Ethylene 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 Methoxy tri-diol ester, isoamyl acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate , Di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate and the like. The hydrocarbon solvent is exemplified by, for example, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, and ring. An aliphatic hydrocarbon solvent such as hexane or methylcyclohexane; benzene, toluene, xylene 'mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, cumene An aromatic hydrocarbon solvent such as diethylbenzene, isobutylbenzene-15-201229067, triethylbenzene, diisopropylbenzene, n-pentylnaphthalene or anisole. Among these, n-butyl acetate, isopropyl acetate, n-amyl acetate, methyl ethyl ketone, methyl n-butyl ketone, methyl n-amyl ketone, methyl pentyl (pentyl) Ketone and anisole 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. By setting the content of the organic solvent in the developing liquid to 80% by mass or more, the contrast of the pattern can be improved by the presence or absence of exposure. As a result, a pattern excellent in development characteristics and lithography characteristics can be formed. Further, the components other than the organic solvent are exemplified by water, eucalyptus oil and the like. An appropriate amount of surfactant may be added to the developing solution as needed. The surfactant is exemplified by an ionic or nonionic fluorine-based and/or lanthanoid surfactant. The development method is, for example, a method in which a substrate is immersed in a bath filled with a developing liquid for a certain period of time (dipping 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 (dipping method). A method of spraying a developing solution onto a surface of a substrate (spraying method), rotating at a constant speed, and scanning a developing solution at a constant speed to apply a developing solution to a substrate (dynamic coating method) )Wait. In the pattern forming method, it is preferred to wash the photoresist 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 by using an organic solvent. The washing liquid is preferably a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent or a guanamine solvent. The -16-201229067 or the like is preferably an alcohol-based solvent or an ester-based solvent, more preferably an alcohol-based solvent having a carbon number of 6 to 8. The one-valent alcohol having 6 to 8 carbon atoms is exemplified by a linear, branched or cyclic one-valent alcohol, and is exemplified by, for example, 1-hexanol, 1-heptanol, 1-octanol, 4-methyl-2- Pentanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octyl alcohol, 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. By setting the water content to 10% by mass or less, good development characteristics can be obtained. Further, an interfacial surfactant to be described later may be added to the washing liquid. The method of the washing treatment is, for example, a method in which a washing liquid is applied onto a substrate that is rotated at a constant speed (a spin coating method), a method in which a substrate is immersed in a tank filled with a washing liquid for a certain period of time (dipping method), and A method of spraying a washing liquid on a substrate 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 and the [B] acid generator. Further, any component may be contained as long as the effects of the present invention are not impaired. Each component is detailed below. <[A] Polymer> [A] The polymer is a polymer having a structural unit (I) of 45 mol% or more and 80 mol% or less. [A] The polymer system selects a small smaller carbon number of 1 to 9 -17-201229067 The protecting group serves as a protecting group, and can be enriched in a small protecting group by containing the structural unit (I) in a specific range, and as a result, The small protecting group can be reduced in surface roughness by exposure post-exposure baking (heating step). In addition, by combining the pattern forming method of the composition and the feature containing the [A] polymer, it is possible to suppress film reduction of the photoresist film excellent in lithographic properties such as CDU, and to form a pattern excellent in lithographic properties. [Structural unit (I)] The structural unit (I) is represented by the above formula (1). In the formula (1), R1 is a hydrogen atom or a methyl group. R2 is a monovalent acid dissociable group and is a linear or branched hydrocarbon group or an alicyclic group. The hydrocarbyl or alicyclic group may contain -0- in the skeleton chain. Further, part or all of the hydrogen atoms of the above alicyclic group may be substituted with a linear or branched hydrocarbon group having 1 to 4 carbon atoms. However, the carbon number in R2 is 1 to 9. The acid dissociable group is a group which substitutes a hydrogen atom in a polar functional group such as a carboxyl group and means a group which is dissociated by the action of an acid generated by exposure to the [B] acid generator. The linear or branched hydrocarbon group represented by R2 is exemplified by a methyl group, an ethyl group, a propyl group, a butyl group or the like. The alicyclic group represented by R2 is exemplified by a monocyclic or polycyclic alicyclic group having a cycloalkane skeleton such as cyclopentane or cyclohexane. Some or all of the hydrogen atoms of the above alicyclic group may be substituted with a linear or branched hydrocarbon group having a carbon number of 丨4. However, since a small protecting group is required, the number of carbon atoms in R2 containing a substituent is from 1 to 9. -18- 201229067 The structural unit (I) is listed as, for example, the test shown below. 【化4】

(wherein R1 is synonymous with the above formula (1)). As for the content ratio of the structural unit in the [A] polymer, the total structural unit constituting the [A] polymer is 45% or more and 8 〇: ear% or less. When the content ratio of the structural unit (I) is less than 45 mol%, there is no possibility that the roughness is reduced. On the other hand, when the content of the structural unit (I) exceeds 80% by mole, the pattern formation property is lowered. Further, the [A] polymer may have one type or two or more types of structural units (!). -19- 201229067 [Construction unit (π)] [Α] The polymer preferably further contains (II). The photoresist film and characteristics can be further improved by bringing the [A] polymer into units. Further, it is possible to increase the resistance of the photoresist film to the lactone skeleton to contain a skeleton containing - (lactone ring). The lactone ring is calculated as a monocyclic group and has other cyclic polycyclic groups. The structural unit (II) is exemplified by a structural unit having a lactone skeleton. • The step contains a structure having a lactone skeleton, and the adhesion of the substrate such as the adhesion of the substrate is soluble. Here, a ring of a bond represented by -c(o)· (a ring, which is said to be a structure only when it is a lactone ring, is not referred to as a structural unit represented by the following formula -20-201229067 [ 5] rL1 rL1 rL1 rL1

-21 - 201229067 [Chem. 6]

RL1

Rl11. ο

ν° (wherein rl1 is a hydrogen atom, a methyl group or a trifluoromethyl group [A] polymer has a structural unit (11) ratio of all structural units of the [A] polymer, preferably 5 moles More preferably, it is 1 5 mol%~60 mol%. When the structural unit (π) is 5 mol%, there will be no increase in the ratio of the resistive film to the substrate. There is a reduction in the formation of the pattern. Also, [A] polymer. or two or more structural units (Π). [Structural unit (III)] [A] The polymer preferably has the above formula. (2 ο ) 0 cases 'relative to the structure % ~ 85 mol %, which contains the ratio of non-adhesiveness. 8 5 mol %, may have one, ) the structure of the structure -22- 201229067 units (III The content ratio of the structural unit is preferably from 1% by mole to 20% by mole. The structural unit (III) can improve the etching resistance of the photoresist film by having a large protective group as a protective group. In the formula (2), R3 is a hydrogen atom or a methyl group. R4 is a group having a monovalent alicyclic group having a carbon number of 10 to 20%. Some or all of the hydrogen atoms of the alicyclic group may be substituted with an alkyl group having a carbon number. The one-valent alicyclic group represented by R 4 is exemplified by a bridged alicyclic group such as a tricyclodecyl group, a tetracyclododecyl group or an adamantyl group. The alkyl group having the above carbon number is exemplified by, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third butyl group. Part or all of one of the hydrogen atoms of the alkyl group may also be substituted with a substituent. The substituent is exemplified by a polar group such as a halogen atom, a hydroxyl group, a carboxyl group or an amine group. The structural unit (III) can suppress the excessive solubility of the organic solvent by having an alkyl group having 1 to 4 carbon atoms substituted by the polar groups, and the shape of the pattern can be improved. The structural unit (III) is listed, for example, as follows. -23- 201229067 【化7】

OH (wherein R3 is synonymous with the above formula (2)). The content ratio of the structural unit (ΙΠ) in the [A] polymer is 10 mol% or more and 20 mol% or less based on the entire structural unit of the [Α] polymer. When the content ratio of the structural unit (III) is in the above range, etching resistance is preferable, and it is preferable. Further, the [Α] polymer may have one type or two or more types of -24-201229067 units (III). [Structural unit (IV)] [A] The polymer has a unit (IV) which has a hydroxyl group by the following formula as long as it does not interfere. There is no particular limitation on the structure of a single hydroxyl group. The structure can also be two or more. Also, the structure is limited. The structural unit (IV) lists the bits. The effect of the present invention may be further configured as a unit (hereinafter sometimes referred to as "configuration (IV)", as long as the number of hydroxyl groups in the unit of the structural unit is a hydroxyl group position in one unit, and is not particularly, for example, the following The structure represented by the statement is -25-201229067 [Chem. 8]

(wherein R5 is a hydrogen atom, a methyl group or a trifluoromethyl group). [A] The content ratio of the structural unit (IV) in the polymer is preferably from 5 mol% to 30 mol%, and more preferably from 1 to 20,0 mol%, based on the total structural unit constituting the [A] polymer. 0 mole %~20 mole%. By including the structural unit (IV) in the [A] polymer, the adhesion of the photoresist pattern to the substrate can be improved, and the collapse of the fine pattern can be suppressed. <[A] Synthesis Method of Polymer> [A] The polymer can be produced by, for example, using a radical polymerization initiator to polymerize a monomer corresponding to each specific structural unit in a suitable solvent. Preferably, for example, a method in which a solution containing a monomer and a radical initiator is added dropwise to a solution containing a reaction solvent or a monomer to carry out a polymerization reaction; and a solution containing a monomer and a radical-containing initiator are used. a method in which a solution is separately added to a solution containing a reaction solvent or a monomer to carry out a polymerization reaction; and a solution containing a plurality of monomers and a solution containing a radical initiator are respectively added dropwise to a reaction solvent or a monomer. It is synthesized by a method such as a polymerization reaction in a solution. The reaction temperature of these methods is preferably determined depending on the type of the initiator. It is usually 30 ° C to 180 ° C, preferably 40 ° C to 160 ° C, more preferably 50. 〇140 it. The dropwise addition time varies depending on the reaction temperature, the type of the initiator, the monomer to be reacted, and the like, but is usually from 30 minutes to 8 hours, preferably from 45 minutes to 6 hours, more preferably from 1 hour to 5 hours. In addition, the total reaction time including the dropping time is the same as the dropping time, and varies depending on the conditions, but is usually 30 minutes to 8 hours', preferably 4 minutes to 7 hours, more preferably 1 hour to 6 hours. . The radical initiators used in the above polymerization are exemplified by azobisisobutyronitrile (AIBN), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2, 2'-Azobis(2-cyclopropylpropionitrile), 2,2,-azobis(2,4-dimethyl-27- 201229067 valeronitrile), 2,2'-azobisisobutyrate Dimethyl acid and the like. These initiators may be used singly or in combination of two or more. The polymerization solvent is a solvent other than a solvent (a nitrobenzene having a polymerization inhibitory effect, a thiol compound having a chain transfer effect, etc.) which hinders polymerization, and is not particularly limited as long as it can dissolve the monomer. The polymerization solvent may, for example, be an alcohol solvent, a ketone solvent, a guanamine solvent, an ester/lactone solvent, a nitrile solvent or a mixed solvent thereof. These solvents may be used singly or in combination of two or more. The resin obtained by the polymerization is preferably recovered by a reprecipitation method. Namely, after the completion of the polymerization reaction, the target resin is recovered as a powder by pouring the polymerization liquid into a reprecipitation solvent. The reprecipitation solvent may be used singly or in combination of two or more kinds of alcohols or alkanes. In addition to the reprecipitation method, low-molecular components such as monomers and oligomers may be removed by a liquid separation operation, a column operation, or an ultrafiltration operation to recover a resin. [A] Polymer The weight average molecular weight (Mw) in terms of polystyrene measured by a gel permeation chromatography (GPC) method is not particularly limited, and is preferably 1, more than 500,000, more preferably 2,000. The above 400,000 or less, preferably 3,000 or more and 300,000 or less. Further, when the Mw of the [A] polymer is less than 1,000, the use as a photoresist tends to be low in heat resistance. On the other hand, when the Mw of the [A] polymer exceeds 50,000,000, the visibility as a photoresist tends to be low. Further, the ratio (Mw/Mn) of the Mw of the [A] polymer to the number average molecular weight (?η) in terms of polystyrene measured by the GPC method is usually 1 or more and 5 or less, preferably 1 or more and 3 or less. It is 1 or more and 2 or less. By making -28- 201229067

Mw/Mn falls within this range, and the photoresist film is excellent in resolution. In the present specification, Mw and Μη are analyzed by GPC column (TOSOH, 2 G2000HXL, 1 G3000HXL, 1 G4000HXL) at a flow rate of 1.0 ml/min, eluting the solvent tetrahydrofuran, and the column temperature is 40 °C. The monodisperse polystyrene is used as a standard, and the [[B] acid generator] is determined by GPC. [B] The acid generating system generates an acid by exposure, and the acid dissociation property in the [A] polymer is utilized by the acid. The base dissociates to produce acid. The form of the [B] acid generator in the composition may be in the form of a compound as described later (hereinafter also referred to as a suitable [B] acid generator), or may be incorporated as a part of the polymer. It can also be the form of the two. The [B] acid generator is exemplified by, for example, a key salt compound, a sulfonium imide compound, a halogen-containing compound, a diazoketone compound, and the like. Among these [B] 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), an iodide salt, an iron salt, a diazo salt, a pyridine pin salt, and the like. The onium salt is exemplified by, for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium 2-bicyclo[ 2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonyl ceramide, 4-cyclohexylphenyldiphenylphosphonium trifluoromethanesulfonate Acid salt, 4-cyclohexylphenyldiphenylphosphonium nonafluorobutane sulfonate, 4-cyclohexylphenyldiphenylphosphonium perfluorooctane sulfonate, 4-cyclohexylphenyl diphenyl锍2-双-29- 201229067 Ring [2.2.1]hept-2-yl-indole, ι,2,2·tetrafluoroethane sulfonate, 4-cyclohexylphenyl diphenyl sulfonate , 4-methanesulfonylphenyldiphenylphosphonium trifluorocarbonate, '4-methanesulfonylphenyldiphenylphosphonium nonafluorobutane sulfonate, 4-ayuan Phenyldiphenylphosphonium perfluoro-n-octane sulfonate, 4-methanesulfonylphenyldiphenylphosphonium 2 -bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetra Fluoride compound, acid salt, 4-methanesulfonylphenyl diphenyl camphorsulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-6-(1-adamantanylcarbonyloxy) - hexane-1-sulfonate or the like. Among these, 'triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butyl compound, 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-?-butoxynaphthalen-1-yl)tetra Hydrothienyl hexafluoro-n-butane sulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene-perfluoro- n-octane sulfonate, 1-(4-n-butoxynaphthalene) -1_yl) tetrahydrothiophene gun 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 gun nonafluoro-n-butane sulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophene gun perfluoro-n-octane sulfonate, 1-(6-positive Butoxynaphthalen-2-yl)tetrahydrothiophene key 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethane sulfonate, b (6-n-butoxy Benazin-2-yl) tetrahydrothiophene mothyl sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene trifluoromethanesulfonate, 1-(3,5 _Dimethyl-4-perphenyl)tetrahydrothiophene nonafluoro-n-butyl compound, 1-(3,5-monomethyl-4-phenylphenyl)tetrazide Key-30- 201229067 perfluoro-n-octane sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene 2·bicyclo[2.2.1]hept-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-n-hexafluoro-n-butane sulfonate, 1-(4-n-butoxynaphthalene-1 The -alkyl)tetrahydrothiophene-perfluoro-n-octanesulfonate and 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene-n-hexafluoro-n-butanesulfonate are preferred. The sulfonium salt is exemplified by, for example, diphenylsulfonium trifluoromethanesulfonate, diphenylsulfonium nine gas n-butyl compound, acid salt, diphenylphosphonium perfluorinated n-antimonate acid salt, diphenylphosphonium 2-bicyclopropane [2.2.1] Hept-2-yl-1,1,2,2·tetrafluoroethanesulfonate, diphenyl anthraquinone sulfonate, bis(4-butylbutylphenyl)iodotrifluoride Methanesulfonate, bis(4_t-butylphenyl)phosphonium nonafluorobutane sulfonate, bis(4-t-butylphenyl) chain perfluoro-n-octane sulfonate, double (4 _T-butylphenyl) town 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethane sulfonate, bis(4-t-butylphenyl) Camphor sulfonate and the like. Among the above sulfonium salts, bis(4-tert-butylphenyl)phosphonium hexafluoro-n-butane sulfonate is preferred. The sulfonimide compound is exemplified by, for example, N.(Trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenine, N-(nonafluoro-n-butane sulfonate)醯oxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenine, N-(perfluoro-n-octanesulfonyloxy)bicyclo[2.2.1]hept-5-ene -2,3-dicarboxylimine imine, heart (2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy)bicyclo[2.2.1] Gh-5-ene-2,3-dicarboxylimideimine 'N-(2-(3-tetracyclo[4·4·〇·1 '5_i7'1Q]12 yards]_ι,ι_difluoro乙院醯醯oxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylimenine, N-(camanosylsulfonyloxy)-31 - 201229067 bicyclo[2.2.1]g -5-ene-2,3-dicarboxylimine, etc. Among the sulfonimide compounds, N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene·2 Preferably, the [B] acid generator may be used alone or in combination of two or more. [B] When the acid generator is an acid generator, the amount of the acid generator is ensured as a photoresist. From the viewpoint of sensitivity and development, it is usually 0.1 parts by mass or more and 20 parts by mass based on 1 part by mass of the [A] polymer. In the case where the amount of the [B] acid generator is less than 0.1 part by mass, the sensitivity and the developing property tend to decrease, and the ratio is preferably 5%. On the one hand, when it exceeds 15 parts by mass, the transparency with respect to the radiation is lowered, and it is difficult to obtain a desired pattern of the photoresist pattern. <Arbitrary component> The linear composition of the sensitive radiation is in addition to the [A] polymer and [ B] A polymer containing a fluorine atom, a solvent, an acid diffusion controlling agent, a biasing accelerator, a surfactant, and an alicyclic skeleton which will be described later, in addition to the acid generator. The compound, the sensitizer, and the like are optional components. Hereinafter, the optional components may be used alone or in combination of two or more. The amount of other optional components may be appropriately determined depending on the purpose. [Polyfluorine-containing polymer] The radiation-sensitive linear resin composition may contain a fluorine atom-containing polymer (excluding [A] polymer). By making the radiation sensitive linear resin composition contain -32-201229067 fluorine-containing atom When forming a photoresist film, the polymer tends to be biased to the vicinity of the surface of the photoresist film due to the oil-repellent characteristics of the fluorine atom-containing polymer in the film, so that the acid generator or the acid generator during the immersion exposure can be suppressed. The acid diffusion controlling agent and the like are dissolved in the liquid immersion medium. Further, by the water repellency characteristic of the fluorine atom-containing polymer, the contact angle of the photoresist film and the liquid immersion medium can be controlled within a desired range, and the bubble can be suppressed. In addition, it is possible to increase the back contact angle between the photoresist film and the liquid immersion medium, so that it is possible to perform high-speed scanning exposure without leaving water droplets. By forming the sensitive radiation linear resin composition with a fluorine-containing atom-containing polymer, a photoresist film suitable for the liquid immersion exposure method can be formed. The fluorine-containing polymer is not particularly limited as long as it has a fluorine atom, but preferably has a fluorine atom content (% by mass) higher than that of the [A] polymer. By making the fluorine atom content higher than that of the [A] polymer, the degree of partialization can be further improved, and the characteristics such as water repellency and dissolution inhibition of the obtained photoresist film can be improved. The fluorine atom-containing polymer in the present invention is formed by polymerizing a monomer containing one or more fluorine atoms in the structure. The monomer having a polymer containing a fluorine atom in the structure is a monomer having a fluorine atom in the main chain, a monomer having a fluorine atom in a side chain, and a monomer having a fluorine atom in both the main chain and the side chain. The monomer which obtains the polymer containing a fluorine atom in a main chain is mentioned, for example, a ct-fluoro acrylate compound, an α-trifluoro methacrylate compound, a β- fluoro acrylate compound, a β- trifluoro methacrylate compound, An α,β-fluoroacrylate compound, an α,β-trifluoromethacrylate compound, a compound in which one or more hydrogens of a vinyl moiety are substituted with fluorine or a trifluoromethyl group, or the like. The monomer obtained by obtaining a polymer having a fluorine atom in a side chain is exemplified by the example -33-201229067. The side chain of the alicyclic hydrocarbon compound such as norbornene is fluorine or a fluoroalkyl group or a derivative thereof, acrylic acid or methyl group. The vinegar compound of a fluoroalkyl group of acrylic acid or a derivative thereof, and a side chain (a site containing no double bond) of one or more olefins are a fluorine atom or a fluoroalkyl group or a derivative thereof. Further, a monomer which obtains a polymer having a fluorine atom in a main chain and a side chain is exemplified by, for example, α·fluoroacrylic acid, β-fluoroacrylic acid, α,β-fluoroacrylic acid, α-trifluoromethacrylic acid, β-three. An ester compound of a fluoroalkyl group or a derivative thereof, such as fluoromethacrylic acid or α,β-trifluoromethylpropane acid, or a compound in which one or more hydrogens of a vinyl moiety are substituted by a fluorine atom or a trifluoromethyl group or the like Where the side chain is substituted by a gas atom or a fluoroalkyl group or a derivative thereof, more than one hydrogen bonded to the double bond of the alicyclic olefin compound is substituted with a fluorine atom or a trifluoromethyl group, and the side chain is halothane. Base or its derivatives. Further, the alicyclic olefin compound is a compound in which a part of the ring is a double bond. The structural unit of the fluorine atom-containing polymer is a structural unit represented by the following formula (3) (hereinafter sometimes referred to as "structural unit (V)").

(In the formula (3), R6 represents hydrogen 'methyl or trifluoromethyl. A is a linking group' and R7 is a linear or branched alkyl group having 1 to 6 carbon atoms containing at least one fluorine atom, or The linking group represented by the carbon number 4 to 20 one-valent alicyclic hydrocarbon group or the derivative thereof -34 to 201229067 A may, for example, be a single bond, an oxygen atom, a sulfur atom, a carbonyloxy group, an oxycarbonyl group or a decylamino group. a sulfonamide group, a urethane group, etc. The monomer which obtains the structural unit (V) is exemplified by, for example, trifluoromethyl (meth)acrylate and 2,2,2-trifluoroethyl (meth)acrylate. Ester, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoroisopropyl (meth)acrylate, perfluoro-n-butyl (meth)acrylate, (meth)acrylic acid Perfluoroisobutyl ester, perfluorotributyl (meth)acrylate, 2-(1,1,1,3,3,3-hexafluoropropyl) (meth)acrylate, (meth)propyl I-enoic acid l-(2,2,3,3,4,4,5,5-octafluoropentyl) ester, perfluorocyclohexyl methyl (meth)acrylate, 1-(2) (meth)acrylic acid , 2,3,3,3-pentafluoropropyl)ester, (meth)acrylic acid 1- ( 3,3, 4,4,5,5,6,6,7,7,8,8,9,9,10,10,1〇-heptadecafluorodecyl)ester, (meth)acrylic acid 1-(5-three Fluoromethyl-3,3,4,4,5,6,6,6-octafluorohexyl) vinegar, etc. The fluorine atom-containing polymer may contain only one structural unit (V), or may contain two or more types. When the content ratio of the structural unit (V) is 1 〇〇 mol% based on all structural units of the fluorine atom-containing polymer, it is usually 5 mol% or more, preferably 10 mol% or more, more preferably When the content of the structural unit (V) is less than 5 mol%, the contact angle of 7 〇 or more cannot be achieved, and the release of the self-resist film such as an acid generator cannot be suppressed. The fluorine atom-containing polymer has, in addition to the above structural unit (V), more than one structural unit having, for example, an acid dissociable group for controlling the dissolution rate of the developing liquid, having a lactone skeleton, a hydroxyl group, a thiol group, etc., -35- 201229067 or "other structural unit" derived from a structural unit of an alicyclic compound, etc. The other structural unit having an acid dissociable group is listed as the above structural unit I) is the same. The structural unit having the lactone skeleton is the same as the structural unit (III). The other structural unit containing the hydroxyl group is the same as the structural unit (IV). Other structural units of the compound of the formula (hereinafter sometimes referred to as "structural unit (VI)") are listed as structural units represented by the following formula (4). [Chemical 1 0] R8 C = 0 (4)

(In the formula (4), R8 represents a hydrogen atom, a methyl group or a trifluoromethyl group. X is an alicyclic hydrocarbon group having 4 to 9 carbon atoms). The above alicyclic hydrocarbon group having 4 to 9 carbon atoms is exemplified by, for example, cyclobutane, cyclopentane, cyclohexane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, tricyclo[5.2 .1.02,6] a hydrocarbyl group formed by an alicyclic ring of a cycloalkane such as decane or tetracyclo[6.2.1.13, 6.02'7]dodecane or tricyclo[3.3.1'7]nonane. The cycloaliphatic ring derived from cycloalkanes may also have a substituent such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl. And one or more substitutions of one or more linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms such as a tributyl group. The monomer which obtains the above structural unit (VI) is exemplified by, for example, (meth)-36-201229067 acrylic-bicyclo[2.2.1]hept-2-yl ester, (meth)acrylic acid-bicyclo[2.2.2]octyl- 2-Based ester, (meth)acrylic acid-tricyclo[5.2.1.0''6]non-7-yl ester, (meth)acrylic acid-tetracyclo[6.2·1.13'6·02'7]dodecane- 9-yl ester, (meth)acrylic acid-tricyclo[3.3.1.13,7]non-1-yl ester, (meth)acrylic acid-tricyclo[3.3.1.I3'7]non-2-yl ester Wait. Preferred monomers for obtaining the other structural units derived from the aromatic compound are exemplified by, for example, styrene, 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-tert-butoxy-α-methylstyrene, 4-(2-B Ethyl-2-propoxy)benzidine, 4-(2-ethyl-2-propoxy)-α-methylstyrene, 4-(ethyloxyethoxy)styrene, 4- (1-ethoxyethoxy)-α-methylstyrene, phenyl (meth)acrylate, benzyl (meth)acrylate, decene, 5-hydroxydecene, 1-B Naphthalene, 2-vinylnaphthalene, 2-hydroxy-6-vinylnaphthalene, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, 1-naphthyl (meth)acrylate Methyl ester, 1-decyl (meth)acrylate, 2-nonyl (meth)acrylate 9-decyl (meth)acrylate, 9-fluorenyl (meth)acrylate, 1- Vinyl phthalocyanine and the like. -37- 201229067 When the content ratio of other structural units is 1 〇〇 mol% based on all structural units of the fluorine atom-containing polymer, it is usually 8 〇 mol% or less, preferably 7.5 mol% or less. More preferably less than 70% by mole. The polymer of the fluorine atom-containing polymer preferably has a ratio of 1 to 50,000, more preferably 1,000 to 30,000 Å, preferably 1,000 to 1 Å, 〇〇〇. When the Mw of the polymer containing a gas atom is less than 1,000, a sufficient front contact angle cannot be obtained. On the other hand, when the Mw exceeds 50,000, there is a tendency for the development of the photoresist to be low, and the ratio of Mw to Μη of the polymer containing fluorine atoms (Mw/Μη) is usually 1-3. Preferably, it is 1 to 2. The content of the fluorine atom-containing polymer in the linear radiation-sensitive resin composition is preferably from 10,000 to 50 parts by mass, more preferably from 20 to 20 parts by mass, based on 100 parts by mass of the [Α] polymer. It is 1 to 1 part by mass, preferably 2 to 8 parts by mass. By setting the content of the polymer of the fluorine atom in the linear radiation-sensitive resin composition to fall within the above range, the water repellency and the dissolution inhibiting property of the surface of the obtained photoresist film can be further improved. [Synthesis method of polymer containing fluorine atom] The fluorine atom-containing polymer can be synthesized by, for example, using a radical polymerization initiator to polymerize a monomer corresponding to each specific structural unit in a suitable solvent. The solvent used in the above polymerization is exemplified by the same solvent as listed in the method for synthesizing the [Α] polymer. The reaction temperature in the above polymerization is usually from 40 ° C to 150 ° C, preferably from -38 to 201229067 50 ° (: ~ 120 °. The reaction time is usually from 1 hour to 48 hours, preferably from 1 hour to 2 4 Hour 〇 [Solvent] The sensitized radiation linear resin composition usually contains a solvent, and the solvent is not particularly limited as long as it can dissolve at least the above [A] polymer, [B] acid generator, and optionally any optional component. The solvent is, for example, an alcohol solvent, a ketone solvent, a guanamine solvent, an ether solvent, an ester solvent, a mixed solvent thereof, etc. The alcohol solvent is exemplified by methanol, ethanol, n-propanol, isopropanol, and 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, second heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, second octanol, ruthenium Alcohol, 2,6-dimethyl-4-heptanol, n-nonanol, second-undecyl alcohol, trimethylnonanol, second-tetradecanol, second heptastanol, decyl alcohol ,phenol, Monoalcoholic solvent such as hexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol or diacetone alcohol; ethylene glycol, 1,2-propanediol, 1,3- Butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl·1,3- a polyvalent alcohol solvent such as hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol or tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl acid, Ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, -39- 201229067 ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, two Ethylene 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 An anthrone-based solvent such as an ether, a propylene glycol monobutyl ether, a dipropylene glycol monomethyl ether, a dipropylene glycol monoethyl ether or a dipropylene glycol monopropyl ether, such as a polyvalent alcohol partial ether solvent, is exemplified by acetone, methyl ethyl Ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, A Isobutyl ketone, methyl n-amyl ketone 'ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl fluorenone, cyclopentanone, cyclohexanone 'cycloheptanone, ring A ketone solvent such as octyl ketone, methylcyclohexanone, 2,4-pentanedione, acetyl ketone, diacetone or acetophenone. The guanamine solvent is exemplified by hydrazine, Ν '-dimethylimidazole. Pyridone, N-methylformamide, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-diethylformamide, acetamidine, hydrazine-methylacetamide, hydrazine, hydrazine-bis Methylacetamide, hydrazine methyl methacrylate, hydrazine-methylpyrrolidone, etc. The ester solvent is exemplified by, for example, diethyl carbonate, propyl 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-methoxy acetate Butyl ester, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-decyl acetate, acetaminoacetic acid Methyl ester, ethyl acetoxyacetate, B Acid ethylene glycol monomethyl ether ester, ethylene glycol monoethyl ether ester, diethylene glycol monomethyl ether acetate, diethylene glycol acetate-40- 201229067 monoethyl ether ester, acetic acid diethyl Alcohol mono-n-butyl ether ester, methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monopropylene glycol dipropylene glycol monoethyl ether ester, diacetic acid Glycol ester, ethylene tri-glycol ester, isoamyl acetate, ethyl propionate, n-butyl isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, n-butyl lactate, N-amyl lactate, diethyl malonate, dimethyl ester, diethyl phthalate, and the like. Other solvents are exemplified by: n-pentane, isopentane, n-hexane, isohexane, n-heptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexanehexane, etc. Aliphatic hydrocarbon solvent; benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylethylbenzene, n-propylbenzene, cumene, diethylbenzene, triethylbenzene, two An aromatic hydrocarbon such as isopropylbenzene or n-pentylnaphthalene, dichloromethane, chloroform, fluorocarbon, chlorobenzene or dichlorobenzene solvent. Among these solvents, propylene glycol monomethyl ether acetate is preferred, and these solvents may be used alone or in combination of two or more. [Acid Diffusion Control Body] The acid diffusion control body controls the diffusion of acid from the [B] acid in the photoresist film by exposure, and exhibits an effect of suppressing the unexposed regional reaction, thereby further improving the obtained linear radiation propylene glycol. A propyl ether ether ether ester, a acid methoxy ester, a propionic acid, a lactic acid ethionic acid, an isoheptane, a methylcyclomethylbenzene, an isobutylbenzene solvent; a halogen-containing cyclohexanone. -41 - 201229067 Storage stability, and further improve the resolution as a photoresist, while suppressing the line of the photoresist pattern due to the change of the placement time from exposure to development processing The composition of the composition is excellent in the stability of the process. The form in which the acid diffusion controlling body is contained in the composition may be in the form of a free compound, or may be a form incorporated as a part of the polymer, or may be in the form of the two. 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, and the like. The amine compounds are exemplified by, for example, mono(cyclo)alkylamines; di(cyclo)-based amines; tri(cyclo)alkylamines; substituted alkylanilines or derivatives thereof; ethylenediamine, N, N , N', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodi Phenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis(4-aminophenyl)propane, 2-(3-amine Phenyl)-2-(4-aminophenyl)propane, 2-(4-aminophenyl)-2-(3-hydroxyphenyl)propene, 2-(4-aminophenyl)- 2-(4-hydroxyphenyl)propane, 1,4-bis(indole-(4-aminophenyl)-1-methylethyl)benzene, 1,3-bis(1-(4-aminobenzene) Base) 1-methylethyl)benzene, bis(2-dimethylaminoethyl)ether, bis(2-diethylaminoethyl)-, 1-(2-aminoethyl)-2 -imidin π ketone, 2- stilbene alcohol, 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-containing third oxonium group is contained. Ee-based compound, amide, N-methylformate 'N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, C醯-42- 201229067 Amine, benzamide, pyrrolidone, N-methylpyrrolidone, N-ethinyl-1-adamantanamine, tris(2-hydroxyethyl) isocyanurate, etc. Listed as, for example, urea, methyl urea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, three N-butyl thiourea, etc. Nitrogen-containing heterocyclic compounds are exemplified by, for example, imidazoles; pyridines; piperazines: pyrazine, pyrazole, pyridazine, quinazoline, indole, pyrrolidine, piperidine, piperidine ethanol, 3-piperidinyl-1,2-propanediol, morpholine, 4-methylmorpholine, 1-(4-morpholinyl)ethanol, 4-ethionylmorpholine, 3-(N-morpholinyl) -1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, etc. Further, as an acid diffusion controlling agent, a weak acid can be used by exposure. a photo-disinfecting base. One example of a photo-disinfecting base is a gun that loses acid diffusion control by exposure decomposition. The salt compound is exemplified by, for example, an onium salt compound represented by the following formula (D1), a salt compound represented by the following formula (〇2), etc. R9 [Chemical Formula 1]

-43- 201229067 (In the formula (D1) and the formula (D2), R9 to R13 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group or a halogen atom, and, in the formula (D1) and the formula (D2), Z· is OH·, R14-COO_, R14-S03_, but R14 is an alkyl group, an aryl group, an alkylaryl group or an anion represented by the following formula (D3). [1 2]

(In the formula (D3), R15 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 〇~2). The content of the acid diffusion controlling agent is preferably less than 5 parts by mass based on 1 part by mass of the [A] polymer. When the total amount is more than 5 parts by mass, the sensitivity as a photoresist tends to decrease. [Positioning accelerator] When the resistive linear resin composition is formed into a resist pattern by a liquid immersion exposure method, a biasing accelerator can be adjusted. By blending the biasing promoter, the polymer containing fluorine atoms can be made closer to the surface layer. [The compound of the ring-shaped skeleton] The compound of the alicyclic skeleton is a component which exhibits an effect of improving the dry etching resistance, the shape of the pattern, and the adhesion to the substrate. -44- 201229067 [Surfactant] The surfactant is a component that exhibits improved coatability and strip action. [Sensitizer] The sensitizer is an energy generator that exhibits absorption of radiation [A] an acid generator to increase the amount of acid generated as the "apparent sensitivity of the linear composition of the sensitive radiation" Modulations> The composition can be prepared, for example, by mixing the optional components of the [A] polymer in a specific ratio with the organic solvent composition to dissolve or disperse in a suitable organic compound. The organic solvent is exemplified as a solvent. The polymer, the [B] acid generator, and the radiation sensitive linear resin composition of any component are usually filtered at a time of use, for example, by a filter having a pore size of about 2 μm, and are motility, development, etc., and the energy is transmitted. To the best, and have the effect of improving. ‘[Β] acid generator, and medium modulation. Further, the state in the solvent is used, and there is no particular limitation as long as it can be dissolved or divided. After the 'dissolved in a solvent, I 〇 [Examples] Hereinafter, the limitations of the examples of the present invention and the like will be specifically described based on examples. However, the present invention is not limited to the use of the <[Α]polymer]-45-201229067 [A] monomer used in the synthesis of a polymer and a fluorine atom-containing polymer described later. 【化1 3】

Ο (M-7) (M-8)

^°^CF3 Ο ο (Μ-13) ( Μ -14)

[Synthesis Example 1] Compound (Ml) 43. lg (50 mol%), and compound (Μ--46 - 201229067 2) 56.9 g (50 mol%) were dissolved in 200 g of 2·butanone, followed by A monomer solution was prepared by adding 5 mol% of 2,2'-azobisisobutyric acid dimethyl ester (4.2 g, 5 mol% based on the total monomers). After injecting a 1000 mL three-necked flask of i〇〇g 2-butanone with nitrogen for 30 minutes, the mixture was heated to 80 ° C while stirring the reaction vessel, and a modified single was added dropwise over 3 hours using a dropping funnel. Body solution. The polymerization was carried out for 6 hours starting from the start of the dropwise addition as the starting time of the polymerization. After completion of the polymerization reaction, the polymerization solution was cooled to 3 ° C or lower by water cooling. The cooled polymerization solution was poured into 2,000 g of methanol, and the precipitated white powder was filtered. After the filtered white powder was washed twice with 400 g of methanol, it was filtered and dried at 50 ° C for 17 hours to obtain a white powdery polymer (A-1) (72.0 g, yield 72.0%). The copolymer had a Mw of 68 50, a hardness of 1.43, and a fluorine atom content of 0.0%. Further, as a result of the analysis of 13^1^11, the polymer (A-1) is a structural unit derived from the compound (Μ-1): the content ratio of the structural unit derived from the compound (Μ-1 2 ) is 49 : 5 1 (mole%) copolymer. The 13C-NMR analysis was carried out by using "JNM-EX400" (manufactured by Sakamoto Electronics Co., Ltd.) and using DMSO as a measuring solvent. [Synthesis Examples 2 to 17] The polymer (A-2) was obtained in the same manner as in Synthesis Example 1, except that each of the monomer compounds of the type and amount shown in Table 1 and the polymerization initiator shown in Table 1 were used. ~ (A-14) and polymer (CA-1) ~ (CA-3). The Mw, Mw/Mn, yield, and residual ratio of the low molecular weight component of each of the obtained polymers and the structural unit content ratio derived from each monomer in each polymer are shown in Table 1-47-201229067 [Table 1]

<Synthesis of a fluorine atom-containing polymer> [Synthesis Example 18] Compound (M-2) 35.8 g (70 mol/〇, and compound (Μ-13) 14.2 Lu (30 mol%) was dissolved in l In 2-butanone of 〇〇g, 2.34 g of dimethyl 2,2'-azobisisobutyrate was added to prepare a monomer solution, and a 500-mL three-necked flask of 20 g of 2-butanone was injected with nitrogen gas. After 30 minutes, the mixture was heated to 80 ° C with stirring, and the prepared monomer solution was added dropwise over 3 hours with a dropping funnel. The polymerization was started as the starting time of the polymerization, and the polymerization was carried out -48-201229067 Reaction 6 After the completion of the polymerization reaction, the polymerization solution was cooled to 30 ° C or lower by water cooling. After the reaction solution was pipetted to a separatory funnel of 1000 mL, the polymerization solution was uniformly diluted with 200 g of n-hexane, and 800 g of methanol was introduced thereto. Then, 20 g of distilled water was added, and the mixture was stirred and allowed to stand for 30 minutes. Then, the lower layer was recovered to obtain a propylene glycol monomethyl ether acetate solution (yield 60%). The copolymer had a Mw of 6, 〇〇 〇, Mw/Mn was 1.45. Further, as a result of 13C-NMR analysis, the polymer (C-1) was derived from the compound. M-2) repeating unit: a copolymer derived from a repeating unit of the compound (M-13) having a ratio of 69: 31 (mol%). <Modulation of a linear radiation-sensitive resin composition> Sensitive radiation linear resin composition The [B] acid generator, the acid diffusion controlling agent, the solvent, and the biasing accelerator used in the preparation of the substance are shown below. [[B] Acid generator] B-1: a compound represented by the following formula [Chemical Formula 1 4 】

ο

F2 C'S03 0 [Acid Diffusion Control Agent] -49- 201229067 D-1 : Compound represented by the following formula [Chemical Formula 15]

E-1: propylene glycol monomethyl ether E-2: cyclohexanone [biasing accelerator] F-1 : γ-butyrolactone [Example 1] Mixed polymer (Α-1) 100 parts by mass, polymerization 5 parts by mass of the compound (C-1), 12.1 parts by mass of the acid generator (Β-1), 1.7 parts by mass of the acid diffusion controlling agent (D_1), 30 parts by mass of the localization accelerator (F-1), and a solvent (E) -1) 1610 parts by mass, (E-2) 690 parts by mass, the resulting mixed solution was filtered through a filter having a pore size of 0.2 μm to prepare a radiation sensitive linear resin composition (S-[Examples 2 to 14 and Comparative Examples 1 to 3) In the same manner as in Example 1, except that each component of the type and amount shown in Table 2 was used, various linear compositions of the radiation sensitive resin were prepared. -50- 201229067 - Linear radiation resin composition of the sensitive radiation [3] Acid generator Fluorine atomic polyacid diffusion inhibitor Fermented female agent - i Media type withdrawal mm Quality part mass parts Type mass parts mm Parts by mass parts Example 1 S-1 A-1 100 Bl 121 C— 1 5 D-1 U F-1 33 E-1/E-2 h 610/69C Example 2 S-2 A—2 100 Bl 12*1 C-1 5 D-1 1.7 F-1 30 Ε-ι/ε-2 1. 610/69C real Example 3 S-3 ~ A-3 100 8-t 12.1 C-1 5 D-1 U F-1 39 E-1/ΐ-*2 1, 610/69C Example 4 S-4 A-4 100 B-1 12.1 C-1 5 D-1 1.7 F-1 30 E-1/E - 2 1. 610/69C Example 5 S-5 A-5 100 B-1 12.1 C-1 5 D-1 T.7 F-1 30 E-1/E-2 1. 610/69C Example 6 S-6 A—6 100 B-1 12.1 C-1 5 D-1 Μ F-1 30 E-1/b 2 1, 610/69C Example 7 S-7 A-7 100 B-1 12.1 C-1 5 D-1 U F-1 30 E-1/E-2 1, 610/69C Example 8 S-8 A-8 100 B—1 12.1 C-1 5 D-1 1.7 F-1 30 Ε-ι/ε 1 2 —·*^ι 1. 610/690 Example 9 S-9 A-9 100 B-1 12.1 5 D-1 t.7 F-1 3C Ε-1/Ε-2 1. 610/69C Example 10 S-10 A-10 100 B-1 12.1 C-1 1 D-1 17 F-1 3C Ε-1/Ε-2 h 610/690 Example 11 S-11 A-11 100 B-1 12.1 C-1 5 D-1 U Fl 30 E-1/ε - 2 t, 610/69C Example 12 S-12 A-12 100 Θ-1 12*1 C-1 5 D-1 1.7 F-1 30 Ε-1/Ε-2 1, 610/69C Example 13 S-13 A-13 100 B-1 12.1 C-1 1 D-1 1-7 F-1 3C El/e-2 1. 610/690 Example 14 S-14 A-14 100 B-1 12.1 C-1 5 D-1 1.7 F- 1 30 E-1/ε-2 1, 610/690 Comparative Example 1 CS-1 CA-1 1 Θ1 1Z1 G-1 5 D-1 U F-1 3C e-1/e-2 1, 610 / 69C Comparative Example 2 CS-2 CA-2 100 B-1 12.1 C-1 5 D-1 U F-1 30 1, 610/690 Comparative Example 3 CS-3 CA-3 100 B-1 12.1 0 to 1 5 D-1 U F-1 30 E-1/E-2 1, 610/690 <Formation of pattern> [Example 15] An anti-reflection film (ARC66' manufactured by 曰 化学 形成 形成 105 105 105 105 105 105 On the 12-inch wafer, the film of the film thickness l〇〇nm formed by the photosensitive radiation composition (S-1) prepared in Example 1 was soft baked at 8 ° C for 60 seconds. Then, using ArF immersion exposure apparatus (NSR S610C, NIKON Corporation), the projection exposure was reduced by a reticle pattern of 220 nm point and 440 nm pitch with NA=1.3, iNA=1.27, ratio = 0.800, quadrupole optical condition. After exposure, post-exposure bake (PEB) was performed at 1 〇 5 °C for 60 seconds. Subsequently, the film was developed with butyl acetate at 23 ° C for 30 seconds, washed with a 4-methyl-2-pentanol solvent for 10 seconds, and dried to obtain a negative resist pattern. At this time, the exposure of the pattern of -55 - 201229067 through the mask pattern of the 440 nm pitch of 220 nm is formed as the optimum exposure amount (E〇P) (mJ/cm2). The measurement is performed using a scanning electron microscope (CG-4000, manufactured by Hitachi High-Technologies). The optimum exposure amount is shown in Table 3. [Examples 16 to 30 and Comparative Examples 4 to 6] The same procedure as in Example 15 was carried out except that the respective radiation-sensitive linear resin compositions described in Table 3 were used, and the PEB temperature was the temperature shown in Table 3. Graphic type. <Evaluation> The following evaluations were made for the patterns formed in Examples 15 to 30 and Comparative Examples 4 to 6. The results are shown in Table 3. Further, "-" in Table 3 indicates that no pattern is formed. [Roughness (nm)] A silicon wafer formed by an ARC66 (manufactured by BREWER SIENCE) underlayer film having an antireflection film having a film thickness of 〇5 nm was used, and a spin coating was carried out using Clean Track ACT12 (Tokyo Electronics Co., Ltd.). The various photosensitive radiation linear resin compositions prepared in the examples and the comparative examples were applied onto a substrate, and PB was formed on a hot plate at 80 ° C for 60 seconds to form a film thickness ο. ιομηι. On the formed photoresist film, an ArF liquid immersion exposure apparatus (S610C, Nikon Corporation's 'inch aperture 1.30') was used, and the optimum exposure amount shown in Table 3 was fully exposed, and pe B 6 was performed at the temperature shown in Table 3. After 0 seconds, the developing solution shown in Table 3 was subjected to a washing treatment at 23 ° C for 30 seconds. The washing treatment was carried out with 4-methyl-2-pentanol for 10 seconds, and dried to form a photoresist film. The surface roughness on the photoresist film was measured by an atomic force microscope (4 0 X 4 0 μηι -52 - 201229067). The roughness measured by RMS was judged as "A (good)" when it was less than 10 nm, and it was judged as "B (bad)" when it was 10 nm or more. [CDU] A total of 30 holes having a diameter of 55 nm formed by the optimum exposure amount shown in Table 3 were measured, and the average deviation of the total of 30 measurement turns was calculated, and 3 times of the enthalpy was calculated as the CDU. When the CDU is less than 4.0, it is judged as "A (good)". When 4.0 or more is less than 5.0, it is judged as "B (slightly good)", and when it is 5.0 or more, it is judged as "C (bad)". [Table 3] Sensitive radiation linear resin composition Developing solution PEB temperature (3⁄4) Optimum exposure (mJ/cm2) Evaluation result Roughness (nm) CDU Example 15 S-1 Butyl acetate 105 18 AA Example 16 S -2 butyl acetate 95 17 AA Example 17 S-3 butyl acetate 105 19 AA Example 18 S-4 butyl acetate 95 16 AA Example 19 S-5 butyl acetate 85 18 AA Example 20 S-6 Butyl Acetate 85 17 AB Example 21 S-7 Butyl Acetate 85 17 AA Example 22 S-8 Butyl Acetate 85 18 AB Example 23 S-9 Butyl Acetate 115 17 AA Example 24 S-10 Ester 100 19 AA Example 25 S-11 Butyl Acetate 105 21 AA Example 26 S-12 Butyl Acetate 90 17 AA Example 27 S-13 Butyl Acetate 95 18 AA Example 28 S-14 Butyl Acetate 90 17 AA Example 29 S-12 methyl-n-pentyl ketone 90 21 AA Example 30 S-12 90 19 AA Comparative Example 4 CS-1 butyl acetate 105 20 BC Comparative Example 5 CS-2 butyl acetate 95 20 BC Comparative Example 6 CS-3 Butyl Acetate 105 — As can be understood from Table 3, according to the pattern forming method of the present invention, the exposure portion after development can be suppressed. Roughness of the surface and the pattern of the excellent CDU-53-201229067 [Probability of industrial use] According to the present invention, it is possible to provide a pattern which suppresses the surface roughness of the exposed portion after development and has excellent lithographic characteristics such as CDU. The formation method, and the sensitive radiation linear resin composition most suitable for the pattern formation method. -54-

Claims (1)

201229067 VII. Patent application scope: 1. A pattern forming method, which comprises a pattern forming method of the following steps: (1) a step of forming a photoresist film on a substrate by using a sensitive radiation linear resin composition, (2) a step of exposing the photoresist film, and (3) a step of developing the exposed photoresist film, wherein the image forming liquid in the developing step contains 80% by mass or more of an organic solvent, Further, the above-mentioned sensitive radiation linear resin composition contains [A] a polymer having a structural unit (I) represented by the following formula (1) in a ratio of 45 mol% or more and 80 mol% or less, and [B] linearity of the sensitivity radiation Acid generator, [Chemical 1] Ο (1) (In the formula (1), R1 is a hydrogen atom or a methyl group, R2 is a monovalent acid-dissociable group, and is a linear or branched hydrocarbon group or an alicyclic group. The hydrocarbon group or alicyclic ring The formula may contain -〇- in the skeleton chain, and 'partial or all of one of the hydrogen atoms of the above alicyclic group may be substituted by a linear or branched hydrocarbon group having 1 to 4 carbon atoms, but in R2 The carbon number is 1~9). The method of forming a pattern according to claim 1, wherein the [A] polymer further contains a structural unit (II) having a lactone skeleton. 3. The pattern forming method according to claim 1 or 2, wherein the [A] polymer further contains a structural unit (III) represented by the following formula (2), and the content ratio of the structural unit (III) is 1〇mol% or more 2〇mol% or less, [Chemical 2] R3 (In the formula (2), R3 is a hydrogen atom or a methyl group, and R4 is a group having a monovalent alicyclic group having a carbon number of 10 to 20, and a part or all of a hydrogen atom of the alicyclic group may be Alkyl substituted with a carbon number of 1 to 4). 4. A sensitive radiation linear resin composition for use in a linear radiation-sensitive resin composition comprising a pattern forming method of the following steps: (1) a step of forming a photoresist film on a substrate using a radiation-sensitive linear resin composition (2) a step of exposing the photoresist film, and (3) a step of developing the exposed photoresist film, wherein the sensitive radiation linear resin composition is characterized by containing [A] by the following formula (丨) The structural unit (I) represented by the ratio is .4 5 mol ° /. More than 80% of the polymer below 80%, and a 56 _ 201229067 [B] sensitive radiation linear acid generator, [Chemical 3] (In the formula (1), R1 is a hydrogen atom or a methyl group, and R2 is a monovalent acid-dissociable group, and is a linear or branched hydrocarbon group or an alicyclic group, and the hydrocarbon group or the alicyclic group may be The skeleton chain contains -〇·, and some or all of the hydrogen atoms of the above alicyclic group may be substituted by a linear or branched hydrocarbon group having 1 to 4 carbon atoms, but the carbon number in R2 is 1~9). -57 - 201229067 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No-3-201229067 V. If there is a chemical formula in this case, please reveal the best display. Chemical formula of the inventive feature: formula (1) -4-