TW201211678A - Radiation-sensitive resin composition - Google Patents

Abstract

Disclosed is a radiation-sensitive resin composition comprising [A] a polymer containing a structural unit (a1) represented by formula (a1) and [B] at least two acid generators each capable of generating a sulfonic acid having an alicyclic backbone carrying 10 or more carbon atoms, wherein the content ratio of the structural unit (a1) in the polymer [A] is 50 mol% or more. In the formula (a1), R1 represents a hydrogen atom or a methyl group, R2 represents an alkyl group having 1 to 10 carbon atoms or a univalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and R3's independently represent an alkyl group having 1 to 10 carbon atoms or a univalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, wherein any two of R3's may be bound to each other to form, together with a carbon atom to which the two R3's are bound, a bivalent alicyclic hydrocarbon group having 4 to 20 carbon atoms.

Description

201211678 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a radiation sensitive linear resin composition. [Prior Art] Conventionally, in the manufacture of semiconductors such as 1C, the manufacture of circuit substrates such as liquid crystals and thermal heads, photolithography using a chemically amplified type of radiation-sensitive linear resin composition is known. The chemically amplified type of radiation-sensitive linear resin composition is irradiated with radiation such as a far-ultraviolet light represented by a KrF excimer laser or an ArF excimer laser, and the radiation portion (exposure portion) generates an acid by the acid. As a reaction of the catalyst, a resist pattern is formed on the substrate by using a difference in the dissolution rate of the developer generated between the exposed portion and the unexposed portion. As for the sensitized radiation linear resin composition, a specific polymer containing an acid dissociable group and an acid generator are known (for reference, Japanese Patent Publication No. Hei. 2-27660). The properties pursued by the acid generator, for example, excellent transparency to radiation, high quantum yield of acid generation, strong acid produced by exposure, and a short diffusion distance of the generated acid in the resist film, resulting in acid It has high compatibility with the resin (polymer) having an acid dissociable group. Among these properties, the structure of the anion portion in the ionic radiation sensitive acid generator is important in order to achieve the strong acid generated, the diffusion distance is appropriately short, and the compatibility of the generated acid with the resin is high. Further, in the nonionic radiation sensitive linear acid generator having a sulfonyl structure or a sulfonate structure, the structure of the sulfonyl moiety is important. -5- 201211678 For example, a resist film formed of a radiation sensitive linear resin composition containing an acid generator having a trifluoromethanesulfonyl structure or a nonafluorobutanesulfonyl structure, the acid produced by exposure is sufficiently strong Acid, as a photoresist, has the advantage of obtaining sufficient sensitivity, but has a long diffusion distance of acid, and has low compatibility with a resin having an acid dissociable group due to a high fluorine content, and has a line width of a resist pattern. Characteristics such as LWR (Line Width Roughness) or Depth Of Focus (DOF: Depth OfFocus) deteriorate. Further, a resist film formed of a radiation sensitive linear resin composition containing an acid generator having a sulfonyl group structure bonded to a 10-organolesulfonyl group-like large organic group has an acid content obtained by exposure The carbon ratio is high enough, the compatibility with the resin having the acid dissociable group is good, and the diffusion distance of the acid is also suitably short, but the strength of the acid is insufficient, and the sensitivity is insufficient, and the sensitivity is insufficient. Insufficient, there is a lack of practicality. As described above, the sensitive radiation linear resin composition has room for improvement, and in particular, development of a resist film material which can form a small LWR and a wide DOF can be formed. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Application Publication No. Hei. No. 2-27660. SUMMARY OF THE INVENTION [Technical Problem] The present invention has been made to solve the above problems, and it is possible to provide a small LWR. The sensitive radiation linear resin composition of the DOF wide resist film is 201211678. [Means for Solving the Problems] The invention to solve the above problems is as follows: A polymer containing [A] a structural unit (ai) represented by the following formula (al) (hereinafter, also referred to as "[A] polymer" And [B] an acid generator having two or more kinds of alicyclic skeletons having a carbon number of 1 or more and producing a sulfonic acid (hereinafter also referred to as "[B] acid generator"), and [A] polymer The structural unit (al) containing a sensitive radiation linear resin composition having a ratio of 50 mol% or more.

(In the formula (al), R1 is a hydrogen atom or a methyl group. R2 is an alkyl group having 1 to 10 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. R3 is independently and is a carbon number of 1 to 10 A mercapto group or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. However, any two R3 bonds may be bonded together with the carbon atoms bonded thereto to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. The [B] acid generator is preferably a compound represented by the following formula (B1). [Chemical 2]

(In the formula (B1), R4 is a monovalent 201211678 hydrocarbon group having an alicyclic skeleton having 10 or more carbon atoms. A is an oxygen atom, a carbonyloxy group or an oxycarbonyl group. X is a carbon number which can be substituted 1 to 20 A divalent linear or branched hydrocarbon group. k is 0 or 1. M + is a monovalent cation.) The above R 4 is preferably a monovalent hydrocarbon group having an adamantane skeleton. The compound represented by the above formula (B1) is preferably a compound represented by the following formula (B1-1). [化3]

(In the formula (B1-1), R5 is a monovalent hydrocarbon group having 1 to 8 carbon atoms which may be substituted. R6 is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms which may be substituted. R7 is independently And a fluorine atom or a perfluoroalkyl group having a carbon number of 1 to 4. A is an oxygen atom, a carbonyloxy group or an oxycarbonyl group. k is 0 or 1. 1 is an integer of 0 to 4. m is an integer of 0 to 10. η is an integer of 1 to 4. M + is a 1 valence cation. However, when R 5 to R 7 are each a plural, the plural R 5 to R 7 may be the same or different.) The above Μ + is represented by the following formula (bl) Preferably, the cation cation or the iodine cation represented by the formula (b2) is preferred. 【化4】

(In the formula (bl), R8 is independently a straight-chain or branched alkyl group having 1 to 10 carbon atoms which may be substituted or an aryl group having 6 to 18 carbon atoms which may be substituted. However, any two The R8 bond, together with the sulfur atom bonded thereto, forms a cyclic structure of -8-201211678, and the remaining R8 may be a linear or branched alkyl group having a carbon number of 1 to 10 which may be substituted or may be substituted. An aryl group having 6 to 18 carbon atoms.) R9-I^R9 (b 2) (In the formula (b2), R9 is independently a linear or branched alkane having 1 to 10 carbon atoms which may be substituted a group or an aryl group having 6 to 18 carbon atoms which may be substituted. However, any two of R9 may be bonded to form a cyclic structure together with the iodine atom to which they are bonded.) The above structural unit (al) is contained The structural unit represented by the following formula (al_l) is preferred. 【化6】

(a 1 - 1) (In the formula (al-Ι), R1 is synonymous with the formula (al). Rl (> is an alkyl group having a carbon number of 1 to 1 。. a is an integer of 0 to 4). [A] The content of the structural unit represented by the above formula (al-Ι) in the polymer is preferably 50% by mole or more. [Effect of the Invention] The sensitive radiation linear resin composition of the present invention can form a small LWR and D Ο [Further Mode of Carrying Out the Invention] <Sensitive Radiation Linear Resin Composition> The radiation sensitive linear resin composition of the present invention contains [A] a polymer and a [B] acid generator. The sensitive radiation linear resin composition may contain, as a suitable component, the [C] acid diffusion inhibitor and the solvent [e] described later. Further, the radiation sensitive linear resin composition may contain other optional components. Hereinafter, each component will be described in detail. <[A] Polymer> [A] Polymer is a polymerization containing 50 mol% or more of the structural unit (al)' represented by the above formula (ai) and accounting for the total structural unit in the [A] polymer Such a polymer may have a high content ratio (50 mol% or more) due to a structural unit having an acid dissociable group. The LWR of the film is reduced. That is, when the acid is generated by the [B] acid generator by irradiation with radiation (exposure), the acid dissociation group is removed, and the acid group of the deprotection is increased. The LWR of the resist film can be made smaller by increasing the solubility in the alkaline developing solution. Further, the sensitive radiation linear resin composition may contain two or more kinds of [A] polymers. [Structural unit (al)] Structure The unit (al) is a structural unit represented by the above formula (ai), and is a structural unit having an acid dissociable group represented by -CR2(R3)2. Such a structural unit having an acid dissociable group is irradiated by radiation ( When the acid is generated by the sensitive radiation linear acid generator, the acid dissociative group is desorbed, and the acidic group - 10, 201211678 is deprotected and becomes acidic. Therefore, the [A] polymer containing a large amount of such an acid dissociable group The solubility of the alkaline developing solution is improved, and in particular, the LWR of the resist film is made small. In the above formula (al), the alkyl group having 1 to 1 carbon atoms represented by 'R2 and R3, for example, Base, ethyl, η-propyl, i-propyl, n-butyl, 1-methylpropyl, 2-methyl Propyl group, t-butyl group, η-pentyl group, η-hexyl group, n-heptyl group, η-octyl 'η-fluorenyl group, η-fluorenyl group, etc. Among these, the acid dissociable group is moderate From the viewpoint of dissociation ability, methyl, ethyl, η-propyl, and i-propyl are preferred. In the above formula (al), a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R2 and optionally 2 The R3 bond, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms formed by the carbon atoms bonded thereto, and examples thereof include cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloglycan. A cycloalkane such as an alkane or a cyclooctane; an adamantane, a bicyclo[2.2.1]heptane, a tricyclo[4.3.0.12,5]nonane or the like having a bridged hydrocarbon skeleton or the like. Among these, it is preferred to have a moderately detachable ability and resolution, and have a skeleton derived from a matrix such as adamantane, cyclopentane, cyclohexane, cyclooctane, etc., having cyclopentane, cyclohexane, cyclooctane. The base of the alkane skeleton is better. [A] The polymer may contain two or more kinds of structural units (al). In terms of the structural unit (al), the structural unit (a 1 -1 ) represented by the above formula (al-Ι) is preferred. When two or more structural units are combined in the structural unit (a 1 ), at least one structural unit (a 1 -1 ) is preferred. In the above formula (al-Ι), the group of the carbon number of 1 to 1 Å represented by R10 may be exemplified by the same group as the alkyl group having 1 to 10 carbon atoms represented by R2 in the above formula (al). Base. -11· 201211678 In the above formula (al-l), a is preferably 1 to 4, more preferably 1 to 2. [A] The content ratio of the 'structural unit (ai) in the polymer is preferably 50 mol% or more, 50 mol% to 80 mol%, and 50 mol% of the total structural unit in the [A] polymer. ~70 mol% is better. When the content ratio of the structural unit (al) is 50 mol% or more, the LWR of the resist film becomes small because the content ratio of the structural unit having an acid dissociable group contained in the [A] polymer becomes high. . On the other hand, when the content ratio of the structural unit (al) is less than 50 mol%, the resolution of the resist film is insufficient, and there is a case where sufficient effect cannot be obtained. [A] In the polymer, the structural unit (al-l) The content ratio is preferably 50 mol% or more of the total structural unit in the [A] polymer, more preferably 50 mol% to 80 mol%, and particularly preferably 50 mol% to 70 mol%. By the content ratio of the structural unit (al-1) being 50 mol% or more, the LWR of the resist film can be made smaller. [Structural unit (a2)] [A] The polymer may contain a structural unit having a lactone structure or a cyclic carbonate structure (hereinafter also referred to as "structural unit (a2)") in addition to the structural unit (al). . Since the polymer [A] contains such a structural unit (a2), the adhesion of the resist film to the substrate is improved, so that the resist pattern becomes difficult to collapse. The structural unit having a lactone structure (hereinafter, also referred to as "structural unit (a2-a)") is exemplified by the following formula (a2-al) to (a2_al6). -12- 201211678

-13- C; «S3' 201211678 In the above formula (a2-al)~(a2-al6), R1 is independently a hydrogen atom or a methyl group. Among these structural units (a2-a), a structural unit having a lactone ring bonded to a polycyclic alicyclic hydrocarbon group is preferred. That is, a structural unit having a lactone ring bonded to a norbornane ring, a structural unit, such as a structural unit (a2-al), (a2-a3), (a2-a7) to (a2-al3) The structural unit having a lactone ring bonded to a bicyclo [2.2.2] octane ring is more preferable, such as (a2-a4). The monomer constituting the structural unit (a2-a) may, for example, be a (meth)acrylic acid-5-oxy-4-oxa-tricyclo[4.2.1.03'7]non-2-yl ester, (methyl) Acyl-9-methoxycarbonyl-5-oxy-4-oxa-tricyclo[4.2.1.03,7]non-2-yl ester, (meth)acrylic acid-5-oxy-4-oxo Hetero-tricyclo[5.2.1.03'8]non-2-yl ester, (meth)acrylic acid-10-methoxycarbonyl-5-oxy-4-oxa-tricyclo[5.2.1.03'8] Ind-2-yl ester, (meth)acrylic acid-6-oxy-7-oxa-bicyclo[3.2.1]oct-2-indole, (meth)acrylic acid-4-methoxycarbonyl-6 -oxy-7-oxa-bicyclo[3.2.1]oct-2-yl ester '(meth)acrylic acid-7-oxy-8-oxa-bicyclo[3.3.1]oct-2-yl ester , (meth)acrylic acid 4-methoxycarbonyl-7-oxy-8-oxa-bicyclo[3.3.1]oct-2-yl ester, (meth)acrylic acid-2-oxytetrafluoropyridinium喃-4-yl ester, 4-methyl-2-oxytetrahydropyran-4-yl (meth) acrylate, 4-ethyl-2-oxytetrahydropyridyl (meth) acrylate Methyl-4-yl ester, 4-propyl-2-oxytetrahydropyran-4-yl (meth)acrylate, (meth) propylene -5-oxytetrahydrofuran-3-yl ester, (meth)acrylic acid-2,2-dimethyl-5-oxytetrahydrofuran-3-yl ester, (methyl)propane-14-201211678 enoic acid-4 , 4-dimethyl-5-oxytetrahydrofuran-3-yl ester, (meth)acrylic acid-2-oxytetrahydrofuran-3-yl ester, (meth)acrylic acid-4,4-dimethyl · 2-oxytetrahydrofuran-3-yl ester, (5) 5-dimethyl-2-oxytetrahydrofuran-3-yl (meth)acrylate, 5-methoxytetrahydrofuran-2 (meth)acrylate -ylmethyl ester, -3,3-dimethyl-5-oxytetrahydrofuran-2-ylmethyl (meth)acrylate, _4,4-dimethyl-5-oxy (meth)acrylate Tetrahydrofuran-2-ylmethyl ester and the like. The structural unit having a cyclic carbonate structure (hereinafter also referred to as "structural unit (a2-b)") may, for example, be a structural unit represented by the following formula (a2-b).

In the above formula (a2_b), R1 is a hydrogen atom or a methyl group. Y is a single bond, a divalent chain hydrocarbon group having 1 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms. Z is a monovalent group having a cyclic carbonate structure represented by the following formula (a2-b'). 【化9】

In the above formula (a2-b,), R1 is a hydrogen atom or a carbon number of 1 to 5! A chain hydrocarbon group. P is 1 or 2. 9 is i or 2. However, where Rii is plural, the plural R11 may be the same or different. 201211678 In the above formula (a2-b), the carbon number represented by γ] is a divalent chain hydrocarbon group of 〜3〇, which may, for example, be a methylene group, an exoethyl group, a propyl group, a hydrazine, or a hydrazine. Basis, butyl, pentyl, hexyl, heptyl, octyl, hydrazine, hydrazine, eleven, ten, ten, ten, ten Fifteen-base, extended sixteen base, extended seventeen base, extended eighteen base, extended nineteen base, extended twenty base and other linear alkyl groups;; _ methyl-丨, 3_ propyl, 2_Methyl_1,3-1,3-propyl, 2-methyl-oxime, 2_propyl, 丨_methyl_丨, 4_butylene, 2-methyl-1,4-butylene , methylene (methylidene), ethylidene (ethylidene), propylidene (propylidene), 2-propylidene (propylidene) and other branched alkyl groups. In the above formula (a2-b), the divalent alicyclic hydrocarbon group having a carbon number of 3 to 3 Å represented by γ may, for example, be a 1,3-cyclopentene butyl group, an i,3-cyclopentylene group or the like, n. a monocyclic cycloalkylene group having a carbon number of 3 to 1 fluorene, such as a cyclohexyl group, a 1,5-cyclohexyl group; a 1,4 -norbornene group (1,4 - n 〇rb 〇rny 1 ene ), 2,5 - a ferrone-based, 1,5-adamantyl, 2,6-adamantyl, and the like, a polycyclic cycloalkyl group, etc., in the above formula (a2-b), a carbon represented by γ The divalent aromatic hydrocarbon group of 6 to 3 Å may, for example, be an extended aryl group such as a phenylene group, a methylphenylene group, an anthranyl group, a phenanthrenyl group or a fluorenyl group. The monovalent group of the cyclic carbonate structure represented by the formula (a2-b) represented by 'z in the above formula (a2-b) (hereinafter, 'may be only described as "Z group") can be mentioned, for example The group in the formula (a2-b) is directly bonded to the cyclic carbonate structure represented by the above formula (a2-b,) (the following structural units (a2-bl) to (a2-b6) are used as a reference) a group having a divalent group between γ -16 and 201211678 in the above formula (a2 b ) (the following structural unit (a2-b7) is used as a reference), and having a ring represented by the above formula (a2-b') The base of the polycyclic structure of the carbonate structure (the following structural units (a2-b8) to (a2-b21) are used as a reference) and the like. Further, the cyclic carbonate structure represented by the above formula (a2-b') in the Z group and the polycyclic structure containing the same may have a substituent (for example, the following structural units (a2-b2), (a2-b5), (a2-b6), (a2-b14), (a2-bl8), (a2-b20) are used as references). The carbon number of the Z group is preferably 3 to 30, more preferably 3 to 15, and particularly preferably 3 to 10. When the carbon number of the Z group exceeds 30, the adhesion of the formed resist film to the substrate is lowered, and the "pour" or "peeling" of the resist pattern is caused. Further, the [A] polymer containing the structural unit (a2-b) having a Z group having a carbon number of more than 30 has a tendency to cause development defects because the solubility in the developer is lowered. In the structural unit (a2-b), for example, a structural unit represented by the following formula (a2-b1) to (a2-b21) is used. -17- 201211678 【化1 0】

(a 2 — b 1) (a 2 — b 2) (a 2 — b 3)

(a 2 - b 1 7) (a 2 - b 1 8) (a 2-b 1 9) (a 2 - b 2 0) (a 2-b 2 l) -18- 201211678 The above formula (a2-bl In the case of ~(a2-b21), R1 is a hydrogen atom or a methyl group. Of these structural units (a2-b), a structural unit (ahbi) is preferred. [A] The polymer may contain two or more types of structural units (a2). The content ratio of the 'structural unit (a2) in the polymer [A] is preferably 20 mol% to 50 mol% of the total structural unit in the [A] polymer. When the content ratio of the structural unit (a2) is within the above range, the formed resist film is excellent in adhesion to the base and has an advantage of improving the resolution of the resist. [A] polymer, in addition to the above structural unit In addition to (ai) or structural unit (a2), other structural units may also be included. The other structural unit is not particularly limited, and examples thereof include a structural unit derived from a (meth) acrylate having a chain hydrocarbon group or an alicyclic hydrocarbon group as a substituent. <[A] Synthesis method of polymer> [A] The polymer can be synthesized by a conventional method such as radical polymerization, and for example, a reaction solution containing each monomer and a radical initiator is dropped to a reaction reaction. a method in which a solvent or a monomer reaction solution is subjected to a polymerization reaction, and a reaction solution containing a monomer and a reaction solution containing a radical initiator are respectively dropped into a reaction solution containing a reaction solvent or a monomer, followed by polymerization. In the method, a reaction solution in which each of the monomers is prepared and a reaction solution containing a radical initiator are dropped into a reaction solution containing a reaction solvent or a monomer, followed by a polymerization reaction. -19- 201211678 The reaction temperature of each polymerization reaction may be appropriately set depending on the type of the initiator, preferably from 30 ° C to 180 ° C, more preferably from 40 ° C to 160 ° C. 5 0 °C ~ MO °C is especially good. The time required for the dropping of various reaction solutions (dropping time) may be appropriately set according to the reaction temperature, the kind of the initiator, the reaction monomer, etc., preferably from 30 minutes to 8 hours, preferably from 45 minutes to 6 hours. 1 hour to 5 hours is especially good. Further, the total reaction time including the dropping time can be appropriately set, but it is preferably 30 minutes to 8 hours, more preferably 45 minutes to 7 hours, and even more preferably 1 hour to 6 hours. When dropping to the reaction solution containing a monomer, the monomer content ratio in the reaction solution is dropped, preferably 30 mol% or more, more preferably 50 mol% or more, and 70 mol%, based on the total amount of the polymerization use monomers. The above is especially good. The radical initiator used for the polymerization may, for example, be 2,2 '-azobis(4-methoxy-2,4-dimethylvaleronitrile) or 2,2'-azobis(2-ring). Propylpropionitrile) '2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisiso-n-butyronitrile, 2,2'-azo double (2· Methyl n-butyronitrile), 1,1,-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2-methyl-N-phenylpropionamidine) dihydrochloride , 2,2'-azobis(2-methyl-N-2-propenylpropionamidine) dihydrochloride, 2,2'-azobis(2-(5-methyl-2-imidazoline) 2-yl)propane) dihydrochloride, 2,2'-azobis(2-methyl-N-(l,l-bis(hydroxymethyl)2-hydroxyethyl)propanamide), Dimethyl-2,2,-azobis(2-methylpropionate), 4,4'-azobis(4-cyanoshikimate), 2,2,-azobis (2_ ( "Hydroxymethyl)propionitrile), etc. These radical initiators may be used alone or in combination of two or more. In the case of the reaction solvent (polymerization solvent) used for the polymerization, a solvent which can dissolve the monomer used in -20 to 201211678 and which is not hindered from polymerization (e.g., nitrobenzene or mercapto compound) can be used without particular limitation. The polymerization solvent may, for example, be an alcohol, an ether, a ketone, a guanamine, an ester, a lactone, a nitrile or a mixed solvent thereof. The alcohol which can be used as a polymerization solvent may, for example, be methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, or 1- Methoxy-2-propanol and the like. The ethers may, for example, be propyl ether, isopropyl ether, butyl methyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, 1,3-dioxane or the like. Examples of the ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone. The guanamines may, for example, be hydrazine, hydrazine-dimethylformamide or N,N-dimethylacetamide. The esters may, for example, be ethyl lactone, methyl acetate or isobutyl acetate such as 7-butyrolactone. Examples of the nitrile include acetonitrile, propionitrile, n-butyronitrile and the like. Further, these solvents may be used singly or in combination of two or more kinds. After the completion of the polymerization reaction, it is preferred to put the polymerization reaction liquid into a re-sinking solvent and recover the powder of the target polymer. The solvent may be, for example, water 'alcohols, ethers, ketones, guanamines, esters, lactones, nitriles, or a mixture thereof. The alcohol which can be used as the re-sinking solvent may, for example, be methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol or 1-methoxy-2-propanol. Examples of the ethers include propyl ether, isopropyl ether, butyl methyl acid, tetrahydrofuran, I,4-dioxane, 1,3-dioxolane, and 1,3-dioxane. Examples of the ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone. Amidoxime, for example, N,N_dimethyl-21 -

J 201211678 carbamide, hydrazine, hydrazine dimethyl acetamide, etc. The ester may, for example, be ethyl acetate, methyl acetate or isobutyl acetate. The lactone may, for example, be r-butyrolactone or the like. Examples of the nitrile include acetonitrile, propionitrile, n-butyronitrile, and the like. The mass average molecular weight (Mw) of the [A] polymer as measured by colloidal permeation chromatography is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and particularly preferably 2,000 to 50,000. When the Mw of the polymer [A] is less than 1,000, the heat resistance of the resist film is lowered. On the other hand, when the Mw of the [A] polymer exceeds 100,000, the developability of the resist film is lowered. Further, the ratio (Mw/Mn) of the Mw of the polymer [A] to the number average molecular weight (?η) is preferably 1 to 5 and more preferably 1 to 3. Further, the polymerization reaction liquid obtained by the polymerization is preferably as small as impurities such as halogen or metal. This is because the impurity content is small, and the sensitivity, resolution, process stability, pattern shape, and the like when forming the resist film can be further improved. The purification method of the polymerization reaction liquid may, for example, be a chemical purification method such as water washing or liquid-liquid extraction, or a combination of such a chemical purification method, a physical purification method such as ultrafiltration or centrifugation, or the like. <[B] Acid generator> The acid generator (B) contained in the linear radiation-sensitive resin composition is an acid generator having two or more sulfonic acid skeletons having a carbon number of 10 or more and producing a sulfonic acid. [B] The acid generator is irradiated with radiation to produce a sulfonic acid having an alicyclic skeleton having a carbon number of 1 Å or more. Due to the action of the sulfonic acid, the [A] polymer has an acid dissociable group detachment and an acidic group deprotection, and the [A] polymer -22-201211678 is soluble in an alkaline developing solution. In this case, the acid generated by the [B] acid generator is a sulfonic acid having a high acidity, and the acid dissociable group of the [A] polymer can be efficiently removed. Further, 'the acid generator produced by [B] and the sulfonic acid produced therefrom are alicyclic skeletons having a carbon number of 10 or more, and the acid generator of [B] and the sulfonic acid produced therefrom become high in boiling point, for example, even in exposure. The pre-baking or post-exposure post-baking or the like is difficult to volatilize and the diffusion is suppressed, that is, the diffusion distance in the resist film is appropriately short. Further, the [B] acid generator and the sulfonic acid produced by the sulfonate having a carbon content of 10 or more have a high carbon content, and have good compatibility with the polymer [A]. The sensitive radiation linear resin composition generally produces two or more kinds of sulfonic acids having different acidity and distribution in the resist film because at least two kinds of acid generators are used. The sulfonic acid has a different distribution in the film thickness direction in the resist film due to the difference in acidity or polarity. Therefore, by producing two or more kinds of sulfonic acids having different acidity and different distribution in the resist film, the acid concentration distribution in the resist film can be controlled, and a pattern having a good squareness can be resolved, and the LWR can be made small. . Further, the DOF can be augmented by adjusting the ratio of the acidity and the sulfonic acid ratio of the two types of sulfonic acids having different distributions in the resist film. Further, the acidity and the distribution in the resist film can be adjusted, for example, by changing the fluorine content of the generated sulfonic acid, etc., to produce an alicyclic skeleton having a carbon number of 1 Å or more. The acid generator of the sulfonic acid is not particularly limited, but a compound represented by the above formula (B 1 ) (hereinafter also referred to as "(B 1 ) acid generator") is preferred. The sulfonic acid produced by such an acid generator can be efficiently improved by the expansion of the -23-201211678 in the resist film, and the solubility of the polymer to the alkali developer can be improved, and the resistance is further increased. The sensitivity and resolution of the film, while making the LWR smaller and the DOF wider. Further, the [B] acid generator is preferably two or more kinds of (B1) acid generators having different structures. In the above formula (B1), the monovalent hydrocarbon group having an alicyclic skeleton having 10 or more carbon atoms represented by R4 may, for example, be adamantane, bicyclo[2.2-1]heptane or tricyclo[4.3.0.12'5]. a monovalent hydrocarbon group having an alicyclic skeleton such as decane or tetracyclo[4.4.0.12'5.17'1()]dodecane. Among these, a monovalent hydrocarbon group having an adamantane skeleton is preferred from the viewpoint of improving the compatibility with the polymer [A]. Further, the monovalent hydrocarbon group having an alicyclic skeleton having a carbon number of 10 or more represented by R4 may be a group formed of an alicyclic skeleton having only 1 or more carbon atoms in the alicyclic skeleton. That is, the alicyclic skeleton is adamantane, and the monovalent hydrocarbon group having an alicyclic skeleton having 10 or more carbon atoms represented by R4 may be adamantyl-1-yl or adamant-2-yl. (B 1 ) The acid generator is preferably a compound represented by the above formula (B 1 - 1) (hereinafter also referred to as "(B 1 -1 ) acid generator"). The preferred combination of the [B] acid generator is a combination of two or more acid generators having different η値 in the above formula (B 1-1). A more preferred combination is a combination of an acid generator of η = 1 and an acid generator of η = 2. In the above formula (Β1-1), when 1 is 1 or more, the monovalent hydrocarbon group having 1 to 8 carbon atoms which may be substituted by R5 may, for example, be a methyl group, an ethyl group or a 1,2-propyl group. N-propyl, η-butyl, η-pentyl, η-hexyl 'η-heptyl, η-octyl or a group in which the hydrogen atoms are substituted. In the above formula, the methyl group and the ethyl group are preferably -24 to 201211678. In the above formula (B1 -1 ), 1 is 1 or more, and the group represented by R5 is not particularly limited to any of the adamantane skeletons. Carbon atom bonding. That is, the adamantane skeleton has a plurality of carbon atoms in the same ring in the plurality of rings, and may bond a group represented by R5, and the adamantane skeleton may have a plurality of (a plural) carbon atoms in the plurality of rings. The bond is represented by the group represented by R5. Further, in the above formula (B1-1), in the above formula (B1-1), the one of the two carbon atoms of the adamantane skeleton may be bonded to each other, and the one is preferably 0 to 3, more preferably 0 to 2, or 0 or 1. good. In the above formula (B1-1), the monovalent hydrocarbon group having 1 to 8 carbon atoms which may be substituted by R6 may, for example, be a methyl group, an ethyl group, a 1,2-propyl group or a η-propyl group η- Butyl, η-pentyl, η-hexyl, η-heptyl, η-octyl and the like. R6 is preferably a hydrogen atom, a methyl group or an ethyl group. In the above formula (Β1-1), R7 is preferably a fluorine atom or a perfluoromethyl group. In the above formula (Β1-1), m is preferably 0 to 8, more preferably 0 to 6, and particularly preferably 1 to 4. In the above formula (B1-1), η is preferably 1 to 3, more preferably 1 or 2. η In the above range, the sulfonic acid produced by the (Β1-1) acid generator has a strong electron-attracting group of a fluorine-containing group at at least the α position of the sulfo group, so that (Β1-1) acid can be obtained. The acidity of the sulfonic acid produced by the generator increases. Further, by changing the ??, the acidity of the (?1-1) acid generator and the distribution in the resist film can be adjusted. In the above formula (Β1-1), when k is 1, Α is preferably a carbonyloxy group. 0 - 25 - 201211678 In the above formulas (B1) and (B1-1), a valence cation represented by M + For example, an anthracene cation such as oxygen, sulfur, selenium, nitrogen, phosphorus, arsenic, chain, chlorine, boron or moth may be mentioned. In the above formula, the iodine cation represented by the above formula (bl) or the iodine cation represented by the above formula (b2) is preferred. In the above formulae (b1) and (b2), R8 or R9 may be substituted. Examples of the linear or branched alkyl group having 1 to 10 carbon atoms include a methyl group and an η-butyl group. In the above formulas (b1) and (b2), the aryl group having 6 to 18 carbon atoms which may be substituted by R8 or R9 may, for example, be a phenyl group or a 4-cyclohexylphenyl group. In the above formulae (b1) and (b2), the group represented by R8 or R9 is preferably an aryl group from the viewpoint of high absorption efficiency of the ray. The phosphonium cation represented by the above formula (b 1 ) is preferably a phosphonium cation represented by the following formula (bl-a) or (bl-b) from the viewpoint of high absorption efficiency of radiation. [1 1]

In the above formula (bl-a), R12 is independently a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted, or an aryl group having 6 to 12 carbon atoms which may be substituted. r is independent, and is an integer of 〇~5. However, when R12 is plural, the plural R12s may be the same or different. In the above formula (bl-b), R13 is a hydroxyl group, a linear or branched alkyl group having a carbon number of 1 -26 to 201211678 to 8 which may be substituted, or an aryl group having 6 to 8 carbon atoms which may be substituted . R14 is a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms which may be substituted, or an aryl group having 6 or 7 carbon atoms which may be substituted. Further, when t is 2 to 6, two of R2 of 2 to 6 may be bonded to each other to form a ring structure. s is an integer of 〇~7. t is an integer of 〇~6. u is an integer from 0 to 3. However, where Rl3 and each are plural, the plural and R14 may be the same or different. The ruthenium cation represented by (bi) is, for example, a phosphonium cation represented by the following formulas (bl-1) to (bK63). [1 2]

-27- 201211678

-28- 201211678 【化1 3】

(b 1 - 2 4) (b 1-25) -29 - 201211678 Ο

Ο (b 1-26) ( b 1 - 2 7) (b 1 - 2 8)

OH OH

(b 1 - 2 9) (b 1-3 0) (bl — 31) (b 1 - 3 2) (bl_33) -30- 201211678

(b 1 -3 4) Cl (b 1 - 3 5)

(bl — 37) (bl—38) (bl — 39) (bl – 40)

(b 1 - 4 2) (b 1 - 4 3) (b 1 - 4 4) (b 1 - 4 5)

(b 1 —4 6) (b 1 -4 7)

H〇^3~sO (b 1-48)

HO^KsQ — O’ (b 1 —4 9) -31 - C: 201211678 [Chem. 1 5]

In the above, the above formulas (bl-1), (bl-2), (bl-6), (bl-8), (b 1 -13 ), (b1 -19 ), (b 1 -25 ) The ruthenium cations represented by (b1-27), (b1-29), (b 1 -33 ), (bl-51), and (bl-54) are preferred. The iodide cation represented by the above formula (b2) is preferably an iodine cation represented by the following formula (b2-a) from the viewpoint of high absorption efficiency of the radiation. -32- 201211678 【化1 6】

The carbon number 6 bond of the previous generation is different from the integer. In the above formula (b2-a), R15 is independently a hydroxyl group, a linear or branched alkyl group which may be 1 to 12, or an aryl group which may be substituted. However, the two aryl groups bonded to the iodine atom may form a cyclic structure together with the iodine atom. ▽ Each is independent, 〇~5. However, when 'R15 is a plural number, the plurality of Ris may be the same as the iodine cation represented by the formula (b2), and may be, for example, an iodine cation represented by the following formula (~(b2-39). -33- 201211678 11 7] 〇~r~〇〇-|+~〇- ^〇-r~〇- (b 2- 1) (b 2- 2) (b 2-3) ΟτΆ Qr<y (b 2-4 ) (b 2 - 5) (b 2-6) (b 2-7) (b 2-8) (b 2- 9) O-'-O-"02 (b 2- 1 0) (b 2 - 1 1) (b 2- 1 2) N02 N〇a 0^·, +Η0 〇2N^Q-rH〇KN02 o2n (b 2— 1 3) (b 2-1 4) (b 2- 1 5 ) Ο^Ό-./ \〇_hO~i+hO~./ 0~rH0^ci (b 2 - 1 6) (b 2- 1 7) (b 2 - 1 8)

Cl Cl

(b 2- 1 9) (b 2-2 0) (b 2-2 1)

(b 2- 2 2) (b 2-2 3) (b 2 - 2 4) -34- 201211678 [Chem. 1 8]

(b 2-2 5) (b 2-2 6) (b 2- 2 7)

(b 2-3 4) (b 2- 3 5;

(b 2 - 3 6) (b 2 - 3 7) (b 2 - 3 8) (b 2-3 9) In the above, iodine represented by the above formulas (b2-l) and (b2-l 1 ) Ruthenium cations are preferred. In the above formula (B 1 ), the iron cation represented by M+ can be produced by a general method described in, for example, Advances in Polymer Science, Vol. 62, ρ·1-48 (1984) -35-201211678. The content of the [B] acid generator is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.1 part by mass to 15 parts by mass, per part by mass of the [A] polymer. When the content of the acid generator (B) is less than 0.1 part by mass, the amount of the sulfonic acid generated is insufficient. Therefore, the acid dissociable group of the [A] polymer cannot be sufficiently deprotected, and the resolution is lowered. On the other hand, when the content of the acid generator (B) exceeds 20 parts by mass, the transparency of the radiation film and the heat resistance of the resist film may decrease, and the shape of the pattern may not be obtained. [C] Acid Diffusion Control Agent > [C] Acid Diffusion Control Agent, which inhibits the diffusion of acid generated by the [B] acid generator in the resist film by irradiation of radiation, and is in the field of non-exposure A side-reactor that inhibits acid from detaching the acid-dissociable group of the [A] polymer. The sensitive radiation linear resin composition has a higher resolution as a resist film by containing such a [C] acid diffusion controlling agent, and can suppress a delay time (PED: Post-Exposure Delay) from exposure to heat treatment. The variation of the line width of the resist pattern caused by the change can obtain a linear radiation resin composition with excellent process stability and storage stability. [C] The acid diffusion controlling agent may, for example, be Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-η-decylamine, Nt-butoxycarbonyldi-n-fluorene. Base amine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N -methyl-1-adamantylamine, (S) - ( - ) -1 - (t-butoxy-36- 201211678 carbonyl)-2-pyrrolidine methanol, (R) - (+ ) butyl)- 2-pyrrolidinemethanol 'Nt-butoxycarbonyl-4-hydroxypiperidine, carbonylpyrrolidine, N,N'-di-t-butoxycarbonylpiperazine, N,]oxycarbonyl-1-gold Alkylamine, hydrazine, hydrazine bis-t-butoxycarbonyl-fluorene adamantylamine, Nt-butoxycarbonyl-4,4'-diaminodiphenyl hydrazine, Ν'-di-t-butoxy Carbonyl exohexyldiamine, N,N,N'N'-tetracarbonylexylhexylamine, N,N'-di-t-butoxycarbonyl-1,7-di,:N,N'-di -t-butoxycarbonyl-1,8-diaminooctane, N,N-oxycarbonyl-1,9-diaminodecane, N,N'-di-t-butoxydecanediamine Base decane, hydrazine, Ν'-di-t-butoxycarbonyl-1,12-di Amine: N,N'-di-t-butoxycarbonyl-4,4'-diaminodiphenylmethaneoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzox An Nt-butoxycarbonyl compound or the like such as butoxycarbonyl-2-phenylbenzimidazole. The acid diffusion controlling agent [C] may, for example, be a tertiary amine compound, a tertiary hydrogen oxide or a nitrogen-containing heterocyclic compound, in addition to the above-mentioned N-t-butoxy compound. The tertiary amine compound may, for example, be triethylamine, tri-n-tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-tri-n-octyl Tri(cyclo)alkylamines such as amine, cyclohexyldimethylamine, dicyclohexylmethylhexylamine; aniline, hydrazine-methylaniline methylaniline, 2-methylaniline, 3-methylaniline, 4 -methylphenylaniline, 2,6-dimethylaniline, 2,6-diisopropylaniline, etc.; alkoxycarbonyl Nt-butyl such as triethanolamine, hydrazine, hydrazine-bis(hydroxyethyl)aniline Oxygen ^ -_ -1 -butylmethyl-1-ylmethane, -t-butoxyamino heptane di-t-butyl:yl-1,10-yldodecane, Nt-butyrazole, N-amine Alkyl carbonyl aminated ammonium propylamine, heptylamine, amine, tricyclic, N,N-diamine, 4-nitroaromatic amine alcohol amine; -37- 201211678 Ν,Ν,Ν',Ν '-Tetramethylethylenediamine, N,N,N',N'-肆(2-hydroxypropyl)ethylenediamine, 1,3-bis(1-(4-aminophenyl)-1- Methyl ethyl) phenylbutanediamine, bis(2-dimethylaminoethyl)ether, bis(2-diethylaminoethyl)ether, and the like. The fourth-order ammonium hydroxide compound may, for example, be tetra-n-propyl hydroxide or tetra-n-butylammonium hydroxide. The nitrogen-containing heterocyclic compound may, for example, be pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine or 2-methyl. Pyridyls such as phenyl pyridine, nicotine, nicotinic acid, nicotinic acid decylamine, quinoline, 4-hydroxyquinoline, 8-hydroxysormine, acridine; piperazine, hydrazine-(2- In addition to piperazines such as hydroxyethyl)piperazine, pyrazine, pyrazole, pyridazine, quinoxaline, indole, pyrrolidine, piperidine, 3-piperidinyl-1,2-propanediol, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, imidazole, 4-methylimidazole, 1-benzyl-2-methyl Imidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, and the like. The [C] acid diffusion controlling agent may be used singly or in combination of two or more kinds. The content of the acid diffusion controlling agent is preferably from 1 part by mass or less, more preferably from 0.001 part by mass to 5 parts by mass, per 100 parts by mass of the polymer of the [A] polymer. When the content of the acid diffusion controlling agent is more than 1 part by mass, the sensitivity of the resist film is remarkably lowered. On the other hand, when the content of the [C] acid diffusion controlling agent is less than 0.001 part by mass, the acid diffusion controlling effect may not be obtained. <Other optional components> -38- 201211678 The radiation sensitive linear resin composition may contain an alicyclic additive having an acid dissociable group, a surfactant, and the like, as long as the effect of the present invention is not impaired. A sensitizer, an alkali-soluble resin, a low molecular alkali solubility control agent having an acid dissociable protecting group, a vignette preventing agent, a storage stabilizer, an antifoaming agent, and the like. Further, other optional components may be combined with each component or two or more of the components. Other optional ingredients are detailed below. (The alicyclic additive having an acid dissociable group) The alicyclic additive having an acid dissociable group is a component having a function of improving dry etching resistance, pattern shape, adhesion to a substrate, and the like. Examples of the alicyclic additive include U-butyl adamantanecarboxylate, t-butoxycarbonylmethyl ester of 1-adamantanecarboxylate, di-t-butyl ester of 1,3-adamantane dicarboxylate, and 1 - adamantane derivatives such as adamantane t-butyl ester, 1-adamantane acetic acid t-butoxycarbonyl methyl ester, 1, 3-adamantane diacetate di-t-butyl ester; deoxycholic acid t- Butyl ester, t-butoxycarbonyl methyl deoxycholate, 2-ethoxyethyl deoxycholate, 2-cyclohexyloxyethyl deoxycholate, 3-oxycyclohexane Deoxycholate such as hexyl ester, tetrahydropyranyl deoxycholate, and mevalonate deoxycholate; t-butyl lithic acid, t-butoxycarbonyl group of lithocholic acid Ester, 2-ethoxyethyl lithocholic acid, 2-cyclohexyloxyethyl lithate, 3-oxycyclohexyl lithate, tetrahydropyranyl lithate, methyl thiocyanate A cholinate such as valeric acid lactone. [Interfacial Agent] The surfactant is a component having an effect of improving coatability, low scratch resistance, and developability -39-201211678. The surfactant may, for example, be polyoxyethylene lauryl ether, polyoxyethylene stearyl decyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octyl phenyl ether, polyoxyethylene η-nonylphenyl group. A nonionic surfactant such as ether or polyethylene glycol dilaurate 'polyethylene glycol distearate. Further, commercially available surfactants include, for example, ΚΡ 3 4 1 (manufactured by Shin-Etsu Chemical Co., Ltd.), Poly flow No. 75, and No. 95 (above, Co., Ltd.), EFTOP EF301, EF303, and EF3 52. (above, manufactured by Thochem Products), MEGAFACE F171, F173 (above, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Fluorad FC430, FC431 (above, Sumitomo 3M), AsahiGuard AG710' Surflon S-382, and SC-101, Same as SC-102, SC-103, SC-104, SC-105, and SC-106 (above, Asahi Glass Co., Ltd.). <Preparation method of sensitive radiation linear resin composition> The radiation sensitive linear resin composition can be obtained by using [A] polymer, [B] acid generator, and [C] acid diffusion controlling agent as a suitable component And the raw material composition of the other optional component is dissolved in the solvent of [E] in such a manner that the total solid content concentration is from 3% by mass to 50% by mass, preferably from 5% by mass to 25% by mass, and is filtered at a pore diameter of about 200 nm. Filtered and modulated. <[E] Solvent> The solvent [E] may, for example, be ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, or ethylene glycol mono-η-propyl ether acetate. Ester, ethylene glycol-40- 201211678 ethylene glycol monoalkyl ether acetate such as mono-η-butyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-η-propyl Propylene glycol monoalkyl ethers such as ether, propylene glycol mono-η-butyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-η-propyl ether, propylene glycol di-η-butyl ether, etc. Alkylene ethers; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-η-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, etc. Ethyl acetate, methyl lactate, ethyl lactate, η-propyl lactate, i-propyl lactate, etc.; formic acid esters such as η-amyl formate and i-pentyl formate; ethyl acetate, Η-propyl acetate, i-propyl acetate, η-butyl acetate, i-butyl acetate, η-amyl acetate, i-pentyl acetate, 3-methoxybutyl acetate, 3-methyl acetate -3-methoxybutyl ester Acetate; i-propyl propionate, η-butyl propionate, i-butyl propionate, 3-methyl-3-methoxybutyl propionate, etc.; Ethyl acetate, ethyl 2-hydroxy-2-methylpropanoate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl butyrate, acetoacetic acid Ethyl esters such as ethyl acetate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, 2-pentanone, 2-hexanone, 2- Ketones such as heptanone, 3-heptanone, 4-heptanone, cyclohexanone; N-methylformamide, N,N-dimethylformamide, N-methylacetamide, hydrazine, hydrazine - decylamines such as dimethylacetamide and hydrazine-methylpyrrolidone; lactones such as τ-butyrolactone. These solvents may be used singly or in combination of two or more. -41 - 201211678 <Resist pattern formation method> A method of forming a resist pattern using the sensitive radiation linear resin composition will be described. A resist film formed of the sensitive radiation linear resin composition (composition solution) is formed on the substrate. Next, the radiation film passing through the hole portion of the mask provided on the optical path is irradiated onto the formed resist film to be exposed. At this time, the acid dissociable group in the [a] polymer is desorbed by the action of the sulfonic acid generated by the [B] acid generator, and the carboxyl group is deprotected. Thus, a carboxyl group is generated, and the solubility of the exposed portion of the resist film to the alkaline developer becomes high. Thereafter, the resist film is developed using an alkaline developing solution, that is, the exposed portion of the resist film is dissolved and removed by the developing solution, and a positive resist pattern can be formed. A suitable coating means such as coating or roll coating is applied to a substrate such as a tantalum wafer or an aluminum-coated wafer to form a resist film. The film thickness of the resist film is preferably from 10 nm to 5,000 nm, preferably from 10 nm to 2,000 nm, and then pre-baked in advance, and then designed to form a mask of a specific resist pattern. The film is exposed. Moreover, the heating condition of the prebaking is changed by the composition of the linear composition of the sensitive radiation, but it is preferably about 30 ° C to 200 ° C, preferably 50 ° C to 150 ° C. . Further, the radiation used for the exposure may be selected from visible light, ultraviolet light, far ultraviolet light, X-ray, charged particle beam, etc., and represented by an ArF excimer laser (wavelength I93 nm) or a KrF excimer laser (wavelength 248 ηηι). The far ultraviolet ray is better, and the ArF excimer laser (wavelength 193 nm) is better. Post-baking after exposure is preferred. By post-baking, the detachment reaction of the -42-201211678 acid dissociable group in the resist film proceeds smoothly. The heating condition of the post-baking is changed by the composition of the linear composition of the sensitive radiation, but it is preferably from 30 ° C to 200 ° C '50 ° C to 170 ° C. In order to exhibit the maximum potential of the sensitizing radiation linear resin composition, an organic or inorganic antireflection film may be formed in advance on the substrate to be used, as disclosed in Japanese Patent Publication No. Hei 6-1 2452. In addition, a protective film may be provided on the resist film as disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. Also, you can use these technologies. Then, by developing the exposed portion of the resist film, a specific resist pattern can be obtained. Developing solution used for developing, for example, to dissolve sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonium water, ethylamine, η-propylamine, diethylamine, two -η-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine 'triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diaza At least one basic selected from the group consisting of heterobicyclo-[5.4.0]-7-fluorene--ene and 15-diazabicyclo-[4.3.0]-5-decene An aqueous solution is preferred. The concentration of the above aqueous alkaline solution is preferably 10% by mass or less. When the concentration of the alkaline aqueous solution exceeds 丨〇 mass % ', the non-exposed portion is also dissolved in the developer. Further, for example, an organic solvent may be added to the developer. The organic solvent may, for example, be a ketone such as acetone, methyl ethyl ketone, methyl i butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone or 2,6-dimethylcyclohexanone. Class; methyl alcohol, ethyl alcohol, η-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1 Alcohols such as 4-hexane dimethylol; tetra-43-201211678 ethers such as hydrogen furan and dioxane; esters such as ethyl acetate and amyl acetate; aromatic hydrocarbons such as toluene and xylene; Dimethylmethaneamine and the like. Further, these organic solvents are used in the above. In the developer, the content ratio of the organic solvent, 100 parts by volume of the phase solution, and more than 100 parts by volume of the total amount of the solvent are more than 100 parts by volume, and the developability is lowered. Further, the developer may be exemplified as an additive in a suitably irradiated linear resin composition. Further, after developing with a developing solution, it is washed with water and then dried. [Embodiment] [Examples] Hereinafter, the present invention will be more specifically described by way of Examples.

Mw and Μη are determined by colloidal permeation chromatography using GPC column, G3000HXL1 branch and G4000HXL1 branch made by Tosoh, with a solvent, tetrahydrofuran, and a column temperature of 4〇t monodisperse polystyrene. Further, the degree of dispersion (Mw/Mn) was determined by the l3C-NMR analysis of the above-mentioned composition using JEOL-EX270. <[A] Synthesis of Polymer> η-butyl ester, acetic acid i-, phenylhydrazine, and acetone base may be used alone or in combination with the above alkaline water. The development of the organic solvent and the exposed portion are preferably added to the sensitive surfactant of the present invention. However, the present invention is not calculated by the measurement condition of (GPC) of the analysis condition of the G2000HXL2 waste amount of 1.0 ml/min. Each of the polynuclear magnetic resonance apparatuses-44 - 201211678 [A] The monomer used for the synthesis of the polymer is as follows Said. [Chem. 1 9]

(Μ—1) (M—2) (M—3) (M—4)

(M-5) (M-6) (M-7) (M-8) (M-9) [Synthesis Example 1] Monomer (M-1) 13_0 g (50 mol%), monomer ( M-7) 2·9 g (l〇mol%), and monomer (M-9)] 0.3 g (30 mol%) dissolved in 60 g of 2-butanone as a polymerization solvent, and further added as a polymerization The starting agent was 2,2'-azobisiso-n-butyronitrile 1.3 g, and the monomer solution (1) was prepared. On the other hand, a monomer solution (2) in which monomer (M-5) 3.8 g (l〇 mol%) was dissolved in 2·butanone (30 g) was placed in a 200-m three-necked flask, and nitrogen gas was blown for 30 minutes. The mixture was heated to 8 (rc, while stirring, and the monomer solution (1) prepared in advance was dropped using a dropping funnel for 3 hours. At the beginning of the dropwise addition, the polymerization reaction was carried out for 6 hours. After the completion of the polymerization reaction, the polymerization solution was allowed to proceed. After cooling to 3 (TC or less) by water cooling, the mixture was poured into methanol of 6〇〇-45-201211678 g, and the precipitated white powder was collected by filtration. The filtered white powder was washed in a slurry of 150 g of methanol twice. Then, the copolymer (A-1) obtained by drying at 50 ° C for 17 hours was obtained. The copolymer (A-1) had Mw of 6,698 and Mw/Mn of I·403, and the yield was 75.3% by mass. Further, the content ratio of the structural unit derived from each monomer in the copolymer (Α-1) measured by 13C-NMR analysis, monomer (M-1) / monomer (M-5) / Monomer (M-7) / Monomer (M-9) was 49.0/9.2/10.1/ 31.6 (mole %). [Synthesis Example 2 to 1 1] Except for the type shown in Table 1, Outside the body Example 1 was similarly operated to synthesize each polymer. Further, each physical property is shown in Table 1. -46 - 201211678 [Table 1] [A] Polymer monomer structural unit content ratio (% by mole) Rate (% by mass) Mw Mw/Mn ratio (mol%) Synthesis Example 1 A-1 M-1 M-5 M-7 M-9 50 10 10 30 49.0 9.2 10.1 31.6 75.3 6,698 1.403 Synthesis Example 2 A -2 M-3 M-5 M-7 M-9 50 10 10 30 49.6 9.3 10.1 31.2 73.4 5,942 1.392 Synthesis Example 3 A-3 M-1 M-6 M-7 M-9 50 10 10 30 49.2 9.1 10.3 31.4 72.6 6,444 1.362 Synthesis Example 4 A-4 M-1 M-5 M-7 M-8 50 10 10 30 49.8 9.7 10.2 30.3 70.2 6,532 1.395 Synthesis Example 5 A-5 M-1 M-5 M-9 50 10 40 49.2 9.3 41.5 75.9 6,549 1.408 Synthesis Example 6 A-6 M-1 M-7 M-9 60 20 20 59.5 20.2 20.3 69.8 7,034 1.392 Synthesis Example 7 A-7 M-1 M-7 M-9 60 10 30 59.6 10.2 30.2 71.3 6,924 1.389 Synthesis Example 8 A-8 M-4 M-7 M-9 60 20 20 50.4 24.9 24.7 60.5 5,349 1.354 Synthesis Example 9 A-9 M-1 M-9 60 40 59.5 40.5 75.8 6,855 1.389 Synthesis Example 10 A-10 M-1 M-9 50 50 49.2 50.8 78.6 6,834 1.384 Synthesis Example 11 A-11 M-2 M-9 50 50 49.1 50.9 75.2 6,593 1.3 76-47-201211678 <Preparation of Sensitive Radiation Linear Resin Composition> The following is a detailed description of each component [B] acid generator B-1 used in the examples and comparative examples: triphenylsulfonium 2·( King Kong Institute-1-yl)-i,i-difluoroacetin-1-sulfonate B-2: triphenylsulfonium 6_(adamantan-1-ylcarbonyloxy)-1,1,2,2 -tetrafluorohexane-1-sulfonate B-3: l-(4-n-butoxynaphthyl)tetrahydrothiophene nonafluoro-η-butanesulfonate Β-4: triphenylsulfonium Perfluoro-η·butane sulfonate 8-5: diphenyl iodide 2-(adamantan-1-yl)-1,1-difluoroethane-1-sulfonate) [C] acid diffusion Inhibitor Cl: Nt-butoxycarbonyl-4-hydroxypiperidine [D] Additive D-1: Fluorinated surfactant [E] Solvent E-1: Propylene glycol monomethyl ether acetate E-2: Ring Hexanone-48-201211678 E-3: r-butyrolactone [Example 1] 100 parts by mass of the mixed copolymer (A-1), (B-1) 3.6 parts by mass of the [B] acid generator And (B-2) 10.6 parts by mass, [C] acid diffusion inhibitor (C-1) as an acid diffusion controlling agent, 1.7 parts by mass, [D] additive (D-1), 0.02 parts by mass, and as a solvent ( E-1) 1 7 parts by mass, (E-2) 700 parts by mass, and (E-3) 30 parts by mass, were filtered through a filter having a pore size of 20 〇ηχη to prepare a radiation-sensitive linear resin composition. [Examples 2 to 16 and Comparative Examples 1 to 6] Each of the sensitive radiation linear resin compositions was prepared in the same manner as in Example 1 except that the components of the type and the amount shown in Table 2 were used. C; 1u' -49 - 201211678 [Table 2] [Α] polymer [曰] acid generator [D] acid diffusion control [D] additive [E] solvent exposure method 1 oh light method 2 surface use S ms ) Surface use; a (mass s) Surface use s (M parts) View s (KS parts) mm. Use s (ΪΪ量) Sensitivity 1 (mJ/cm*) DQF1 LWRI Sensitivity 2 D0F2 LWR2 Bao Shi 1 Α-1 100 B-1 B-2 3.6 10.6 Cl 1.7 D-1 0.02 El E-2 E-3 1, 700 700 30 36 AA 24 AAS Example 2 Α-1 100 Bt 8-2 4.8 9.1 Cl 1.6 Dl 0.02 E-1 E-2 ζ-3 1. 700 700 30 36 AA 26 AA Η Example 3 Α-1 100 B-1 0-2 6.0 7.6 C-1 1.6 D-1 0.02 El E-2 E- 3 1. 700 700 30 38 AA 27 AA Example 4 Α-2 100 B-1 B-2 3.6 10.6 0-1 1.7 Dl 0.02 E-1 E-2 E-3 1. 700 700 30 36 AA 25 AA Example 5 Α-3 10Q B-1 B-2 3.6 10.6 Cl 1.7 D-1 0.02 E-1 E-2 e-3 1. 700 700 30 34 AA 23 AA Example 6 Α-4 100 B-1 B -2 3.6 10.6 C-1 1.7 D-1 0.02 ε-1 E-2 ε-3 I. 700 700 30 36 AA 24 AA 0 Example 7 Α-6 100 B-1 B-2 3.6 10.6 0-1 1.7 D-1 0.02 El E-2 E-3 1. 700 700 30 37 AA 26 AA Cargo 8 Α-6 100 B-1 B-2 10Λ 3.9 0-1 t.2 D- 1 0.02 El E-2 E-3 ί. 700 700 30 31 AA 20 AA Example 9 Α-Θ 100 B-1 B-2 9.6 3.0 C-1 1.3 0-1 0.02 E-1 E-2 E- 3 1, 700 700 30 29 AA 18 AA 贲10 Α-7 100 B-1 B-2 10.4 3.9 C-1 1.2 D-1 0.02 E-1 E-2 E-3 ί. 700 700 30 32 AA 21 AA Example 11 Α-8 100 B-1 B-2 10.4 3.9 C-1 1.2 D-1 0.02 E-1 E-2 E-3 1. 700 700 30 31 AA 20 AA Example 12 Α-9 100 B-1 B-2 10.4 3.9 Cl 1.2 D-1 0.02 et e-2 E-3 t. 700 700 30 34 AA 23 AA Example 13 Α-1 0 100 B-1 0-2 10.4 3.9 C-1 1.2 0-1 0.02 El E-2 E-3 1. 700 700 30 31 AA 20 AA Cargo 14 Α-1 1 100 B-1 B-2 10.4 3.9 C-1 1.2 D-1 0.02 £-1 E -2 E-3 t, 700 700 30 31 AA 20 AAS Example 15 Α-1 100 B-5 B-2 3.6 10.6 C-1 1.7 D-1 0.02 E-1 E-2 E-3 1. 700 700 30 40 AA 29 AA 1616 Α-6 too Θ-5 B-2 10.4 3.9 C-1 1.2 D-1 0.02 E-1 E-2 E-3 1, 700 700 30 36 AA 26 AA , Comparative Example 1 Α-1 100 B-1 12.0 Cl 1.6 D-1 0.02 E-1 e-2 E-3 1. 700 700 30 40 曰B 39 B Θ Comparative Example 2 Α-1 100 B-2 12.6 Cl 1.6 D- 1 0.02 E-1 E-2 E-3 1. 700 700 30 31 Θ 8 20 曰B Comparative Example 3 Α-1 too B-3 12.0 C-1 1.6 D-1 0.02 E-1 E-2 E-3 1, 700 700 30 28 BA 17 6 A 1 Comparative Example 4 1 Α-1 100 B-4 12.0 Cl 1.6 D-1 0.02 El E-2 E-3 1. 700 700 30 26 QB 16 Θ 6 Comparative Example 5 Α-1 100 B-1 B-3 3.6 10.6 C-1 1.6 D-1 0.02 E-1 E-2 E-3 t, 700 700 30 30 BA 19 QA Comparative Example 6 Α-1 100 Day-1 B-4 3.6 10.6 Cl 1.6 D-1 0.02 E-1 E-2 ξ-3 1, 700 700 30 28 Θ B 17 Θ Θ -50-201211678 <Evaluation> Using the respective lipid compositions of Examples 1 to 16 and Comparative Examples 1 to 6, the following characteristics were evaluated. For the evaluation results, for example, (1) Exposure Method 1 [Sensitivity 1 (m J / c m2 )] A radiation linear resin having a film of ARC2 9 (manufactured by Nissan Chemical Industries, Ltd.) as a lower layer of 7 7 nm is formed on the surface of the tantalum wafer. The composition was coated with a coating by spin coating, and baked at 100 ° C for 60 seconds to form a resist film formed by a film thickness of 90 nm. ArF excimer laser exposure was used. 3 06C, the number of openings is 0.78), after exposure for two seconds through the mask, after baking, it is immersed in 2.38% tetramethyl hydroxide at 23 ° C for 60 seconds, developed, washed, dried and shaped. . At this time, the resist pattern imaged by the mask of the line 1L1S) having a design size of 90 nm is made into a light amount of 90 nm as the optimum exposure amount (hereinafter, also referred to as "the best exposure, the optimum exposure amount (mJ/). Cm2) as the sensitivity. Further, the post-baking is performed at 50 ° C for 60 seconds. In this specification, the type refers to a pattern of a certain width of the line portion and a certain width of the interdigitation pattern. Also, the line/pitch pattern (1) L 1 S ) means that the ratio of the width of the line portion is "1: 1 j line/pitch pattern. The t line/pitch pattern (1 LI S) refers to the line of the line sensitive radiation linear tree of 90 nm wide. The film thickness of the reflective film is PTC8 (the resist film of Tokyo hot metal plate. It is placed in Ni (manufactured by Nikon, 60 ° ammonium solution at 95 ° C, in a positive resist / pitch pattern) (1 LIS exposure amount 1)), the line/pitch pattern of the embodiment 13 is arranged in parallel with the width and the pitch R, that is, 90 nm and width 90 ηηι -51 - 201211678 Resistive pattern type [LWR1] The 90nm line/pitch pattern (1L1S) formed by the above-mentioned optimum exposure amount is used for length measurement SEM (S9380, Hitachi) In the SEM image, 'the line width is measured at any 50 points, and the unevenness is expressed as 3 σ値'. 3 σ値 is below 9 · Onm. ( (Just judged to be good)' 3 When σ値 exceeds 9.0 nm, it is “B” (determined as defective). Here, “3 σ値” means that the standard deviation of the measurement result at any 50 points is 3 times. D [D0F1] The size of the line/pitch pattern with the above-mentioned optimum exposure amount 1 is the focus of the mask design size (9 Onm ) within ±10% (ie, 80 to 100 nm). The amplitude (focus depth) is DOF (nm), the DOF is "A" when the value is 300 00 nm or more (it is judged to be good), and the case where the DOF is less than 300 nm is "B" (determined as defective). (2) Exposure method 2 [sensitivity 2 (mJ/cm2)] First, a film thickness of 120 nm was formed on each of the 12-inch wafers on which the lower-layer anti-reflection film ("ARC66", manufactured by Nissan Chemical Co., Ltd.) was formed. The film was soft baked (SB) for 60 seconds at 100 degrees. Then, the film was made of ArF excimer laser Exposure-52-201211678 ("NSRS610C", manufactured by NIKON Corporation), through the pattern of 45nm Line90nm Pitch, with NA=1.3, iNA= 1.27, ratio= 0.800, DipoleX ( Blade Angle 35 degrees), and polarized light conditions A mask pattern (6% half tone) is used for exposure. After the exposure, the respective radiation-sensitive resin compositions were post-baked (PEB) at 95 ° C for 60 seconds. Thereafter, development was carried out with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, washed with water, and dried to form a positive resist pattern. At this time, the exposure amount of the line formed by the mask pattern formed by the 45 nm Line 90 nm Pitch is 45 nm as the optimum exposure amount (hereinafter, also referred to as "optimal exposure amount 2"), and the optimum exposure is performed. The amount (mJ/cm2) is the sensitivity. Further, the post-baking of Example 13 was carried out at 10 ° C for 60 seconds. Measurement length using a scanning electron microscope ("CG-4000", manufactured by Hitachi High-Technologies Co., Ltd.) 〇 [LWR2] A 45 nm line/pitch pattern (1L1S) formed with the above optimum exposure amount 2 was used for the length measurement SEM ( S9380, manufactured by Hitachi, Ltd.), from the top of the pattern. In the S EM image, the width of the line portion is measured at any 50 points, and when the unevenness is expressed as 3 σ ,, the case where 3 σ 値 is below 4. Onm is "A" (determined to be good). 3 The case where σ値 exceeds 4.〇nm is “B” (determined as defective). [DOF2] The line/pitch pattern size obtained by the above-mentioned optimum exposure amount 2 is -53-201211678 in the range of 10% of the design size (45 nm) of the mask (that is, 40_5 to 49.5 nm). The focus amplitude (focus depth) is DOF (nm), the DOF is "A" when it is 240 nm or more (it is judged to be good), and the case where the DOF is less than 240 nm is "B" (determined as defective). From the results of Table 2, it can be understood that the content of the structural unit (al) having an acid-dissociable group is more than 50% by mass of the [A] polymer in the [A] polymer and two or more types having a specific skeleton. The sensitive radiation linear resin composition of the [B] acid generator can form a resist film having a small LWR and a wide DOF as compared with the radiation sensitive linear resin composition of the comparative example. [Industrial Applicability] The sensitive radiation linear resin composition of the present invention is a material suitable for use in a photoresist which is increasingly required to have a line width of a resist pattern. -54-

Claims (1)

201211678 VII. Patent application scope: 1. A sensitive radiation linear resin composition characterized by containing [A] a polymer having a structural unit (ai) represented by the following formula (al), and [B] having a carbon number of 1 〇 The above alicyclic skeleton produces two or more acid generators of sulfonic acid, and the content ratio of the structural unit (al) in the [A] polymer is 50 mol% or more, [Chemical 1] (In the formula (al), R1 is a hydrogen atom or a methyl group, r2 is a carbon number of &~" or a monovalent alicyclic hydrocarbon group having a carbon number of 4 to 20, and r3 is independently independent, and has a carbon number of 1 to 10 a hospital base or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, but any two R 3 linkages together with the carbon atoms bonded thereto form a divalent alicyclic ring having a carbon number of 4 to 20. Hydrocarbyl). 2. The sensitive radiation linear resin composition according to claim 1, wherein the 'B' acid generator is a compound represented by the following formula (B1), which is 2) (In the formula (B1), R4 is a monohydrocarbyl group having an alicyclic skeleton having 1 or more carbon atoms, A is an oxygen atom, a carbonyloxy group or an oxycarbonyl group, and hydrazine is a carbon number which can be substituted -55-201211678 a linear or branched hydrocarbon group of 2 to 20 valence, k is 0 or 1, and Μ + is a monovalent cation). 3. The radiation sensitive linear resin composition according to claim 2, wherein the above R4 is a monovalent hydrocarbon group having an adamantane skeleton. The sensitive radiation linear resin composition according to claim 2, wherein the compound represented by the above formula (Β1) comprises a compound represented by the following formula (Β1-1), [Chemical 3] (In the formula (Β1-1), 'r5 is a monovalent hydrocarbon group of the carbon number 1 to 8 which can be substituted 'R0' is independently a hydrogen atom or a monovalent nicotinyl group of R 1 to 8 which can be substituted. Independently, it is a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and octa is an oxygen atom, a carbonyloxy group or an oxycarbonyl group, k is 0 or 1, and 1 is an integer of 0 to 4 'm is 〇~10 An integer, η is an integer of 1 to 4, and M + is a monovalent iron cation. However, when R5 to R7 are each a plural number, the plural R5 to R7 may be the same or different. 5' $2 The sensitive radiation linear resin composition, wherein 'the stomach is represented by the following formula (b1) or the iron iodide represented by the formula (b2), R4 (b 1) R8 ( In the formula (bi), 'rS is independent, and is a linear or branched alkyl group of a carbon number ι~ι〇-56-201211678 which may be substituted or an aryl group having a carbon number of 6 to 18 which may be substituted, but Any two R8 bonds, together with the sulfur atom bonded thereto, form a ring structure, and the remaining R8 may be a linear or branched alkyl group which may be substituted with a carbon number of 1 to 〇 Substituted aryl group having a carbon number of 6 to 18) R5_, ±_R9 (b 2) (In the formula (b2), R9 is independently a linear one which may be substituted with a carbon number of 1 to 1 Å or A branched alkyl group or an aryl group having 6 to 18 carbon atoms which may be substituted 'but 'any two R 9 may be bonded 'to form a cyclic structure together with the iodine atom to which they are bonded). The sensitive radiation linear resin composition according to claim 1, wherein the structural unit (al) includes a structural unit represented by the following formula (al-1), [Chem. 6] In ι-d work al-l), Ri is synonymous with the formula (al), R10 is a carbon number of 1 to 1 ί π; base, a is an integer of 0 to 4). (5) The sensitive radiation linear resin composition according to Item 6, wherein the content of the structural unit represented by the above formula (q) in the [A] polymer is 50% by mole or more. -57- 201211678 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the symbol of the representative circle is simple: No 201211678 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention. :no