JP2007128104A - Resist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hyperbranched polymer suitable as a polymer material for nanofabrication, in particular, photolithography, and to provide a hyperbranched polymer having an acid decomposition group at the end of a molecule of the hyperbranched polymer obtained by a living radical polymerization reaction of a styrene derivative. <P>SOLUTION: The hyperbranched polymer has a core portion prepared by a living radical polymerization of chloromethyl styrene or the like, and an acid decomposition group such as p-tert-butoxy styrene, which is linked to the core portion and present at the end of a molecule of the polymer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a hyperbranched polymer suitable as a polymer material for nanofabrication centering on optical lithography, a method for producing the same, and a hyperbranched polymer as a base polymer for a resist material. The present invention relates to a resist composition capable of forming a pattern.

  In recent years, optical lithography, which is regarded as promising as a microfabrication technology, has been miniaturized by shortening the wavelength of a light source, and has realized high integration of VLSI. Therefore, for the resist composition, development of a base polymer having a chemical structure transparent to each light source is in progress. For example, with KrF excimer laser light (wavelength 248 nm), a polymer having PHS (polyhydroxystyrene) as a basic skeleton, with ArF excimer laser light (wavelength 193 nm), an alicyclic polymer, or F2 excimer laser light (wavelength 157 nm) A resist composition containing a polymer into which a fluorine atom (perfluoro structure) is introduced has been proposed (see WO 00/17712).

  However, when the polymer is applied to the formation of ultrafine patterns of 50 nm or less, which will be required in the future, the unevenness of the pattern side wall using the line edge roughness as an index has become a problem. Franco Cerrina, Vac. Sci. Tech. B, 19, 62890 (2001), a conventional resist mainly composed of PMMA (polymethylmethacrylate) and PHS (polyhydroxystyrene) is exposed to an electron beam or extreme ultraviolet (EUV), and is exposed to 50 nm or less. In order to form a fine pattern, it has been pointed out that it is a problem to control the surface smoothness at the nano level.

  Toru Yamaguchi, Jpn. J. et al. Appl. Phys. , 38, 7114 (1999), the unevenness of the pattern side wall is attributed to an aggregate of polymers constituting the resist, and many reports have been made on techniques for suppressing the molecular assembly of the polymer.

  For example, Toru Yamaguchi, Jpn. J. et al. Appl. Phys. , 38, 7114 (1999), it is reported that the introduction of a crosslinked structure into a linear polymer is effective as a means for improving the surface smoothness of a positive electron beam resist.

  In addition, as an example of a branched polymer that has improved line edge roughness as compared with a linear molecule, JP 2000-347612 discloses a polymer in which a main chain of a linear phenol derivative is branched and linked. However, pattern formation of 50 nm or less has not been achieved.

Also, Alexander R. Trimble, Proceedings of SPIE, 3999, 1198, (2000) discloses a branched polyester made of a phenol derivative having a carboxyl group, but has poor adhesion to a substrate.
JP 2000-00516 A, JP 2000-514479 A, Krzysztof Matyjazewski, Macromolecules 29, 1079 (1996) and Jean M. et al. J. et al. Frecht, J .; Poly. Sci. , 36, 955 (1998), it is reported that the degree of branching and weight average molecular weight of living styrene polymerization of chloromethylstyrene can be controlled with respect to high branching of styrene derivatives, which are the main polymer of lithography. Has been.

  However, until now, there has been no report on molecular design for imparting processability by exposure, which is necessary for resists, and the present situation is that rapid development is desired.

  The present invention relates to a hyperbranched polymer with improved surface smoothness and alkali solubility that can be used as a polymer material for nanofabrication centered on photolithography, a method for producing the hyperbranched polymer, An object of the present invention is to provide a resist composition containing the resist composition.

  As a result of intensive studies by the present inventors in order to solve the above problems, the following knowledge has been obtained. That is, a hyperbranched polymer having an advanced branch structure as a core and an acid-decomposable group at the molecular end has a small molecular entanglement seen in a linear polymer and a molecular structure that crosslinks the main chain. It was found that the swelling by the solvent was also small. As a result, it was found that the formation of large molecular aggregates that cause surface roughness on the pattern side wall is suppressed. In addition, the hyperbranched polymer usually takes a spherical form. However, when an acid-decomposable group is present on the spherical polymer surface, in photolithography, a decomposition reaction occurs due to the action of an acid generated from the photoacid generator at the exposed portion, and hydrophilicity occurs. As a result of the formation of groups, it was found that a spherical micelle-like structure having a large number of hydrophilic groups on the outer periphery of the polymer molecule can be taken. As a result, it was found that the polymer is efficiently dissolved in an alkaline aqueous solution and removed together with the alkaline solution, so that a fine pattern can be formed and can be suitably used as a base resin for a resist material.

  The present invention has been made based on the above findings of the present inventors. That is, this invention provides the hyperbranched polymer characterized by having an acid-decomposable group at the polymer molecule terminal.

  The present invention also provides a hyperbranched polymer having an acid-decomposable group at the molecular end of a hyperbranched polymer obtained by subjecting a styrene derivative to a living radical polymerization reaction.

  In the present invention, the core portion in the hyperbranched polymer is a homopolymer of a monomer represented by the following formula (1), or a monomer represented by the following formula (1) and the following formula (2) to (5) It is preferably a copolymer with at least one monomer selected from

  (In Formula (1), Y represents a C1-C10 alkylene group which may contain a hydroxyl group or a carboxyl group. Z represents a halogen atom.)

(In the formulas (2) to (5), R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
R ² and R ³ represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and R ² and R ³ are the same or different from each other. May be.

R ⁴ represents a hydrogen atom; a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms; a trialkylsilyl group (wherein each alkyl group has 1 to 6 carbon atoms); an oxoalkyl group ( Here, the carbon number of the alkyl group is 4 to 20); or a group represented by the following formula (6) (wherein R ⁵ is a linear, branched or cyclic carbon number of 1 to 10). An alkyl group, R ⁶ and R ⁷ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or R ⁶ and R ⁷ are linear or branched; When a chain-like alkyl group having 1 to 10 carbon atoms is represented, they may be combined with each other to form a ring). n represents an integer of 0 to 10. )

  In the present invention, the monomer represented by the formula (1) may be subjected to living radical polymerization alone, or at least one selected from the monomer represented by the formula (1) and the formulas (2) to (5). And a step of introducing an acid-decomposable group into the polymer by reacting the polymer obtained in this step with a compound containing an acid-decomposable group. A method for producing a hyperbranched polymer is provided.

  The present invention also includes a hyperbranched polymer synthesis step for synthesizing a hyperbranched polymer by subjecting a monomer represented by the following formula (1) to a living radical polymerization reaction, and a compound containing an acid-decomposable group from the synthesized hyperbranched polymer. And a step of introducing an acid-decomposable group into the terminal of the hyperbranched polymer to introduce an acid-decomposable group, thereby providing a method for producing a hyperbranched polymer.

  (In Formula (1), Y represents a C1-C10 alkylene group which may contain a hydroxyl group or a carboxyl group. Z represents a halogen atom.)

  The present invention also provides a resist composition containing the hyperbranched polymer.

  According to the present invention, various problems in the prior art can be solved, a hyperbranched polymer that can be used as a polymer material for nanofabrication centered on optical lithography, and an electron beam whose surface smoothness is required on the nano order, Provided is a resist composition containing a hyperbranched polymer that is suitable as a base polymer for resist materials compatible with deep ultraviolet (DUV) and extreme ultraviolet (EUV) light sources and capable of forming fine patterns for VLSI manufacturing. it can.

  ADVANTAGE OF THE INVENTION According to this invention, the base polymer of the resist material which improved surface smoothness and alkali solubility can be provided. According to the present invention, it is also possible to provide a base polymer of a resist material which is excellent in sensitivity, etching resistance and film formability and is less contaminated with a metal catalyst or the like.

(Manufacturing method of hyperbranched polymer and hyperbranched polymer)
The hyperbranched polymer of the present invention has an acid-decomposable group at the end of the core portion of a highly branched structure.

  The hyperbranched polymer of the present invention has an acid-decomposable group at the molecular terminal of a hyperbranched polymer obtained by subjecting a styrene derivative to a living radical polymerization reaction.

  The hyperbranched polymer of the present invention can be obtained by the method for producing a hyperbranched polymer of the present invention.

  The method for producing a hyperbranched polymer of the present invention includes a core synthesis step and an acid-decomposable group introduction step, and includes other steps as necessary.

  Hereinafter, the details of the hyperbranched polymer of the present invention will be clarified through the description of the method for producing the hyperbranched polymer of the present invention.

-Core part synthesis process-
The monomer for forming the core portion of the hyperbranched polymer of the present invention is not particularly limited as long as living radical polymerization is possible, and can be appropriately selected according to the purpose. For example, those represented by the above formulas (1) to (5) are suitable.

  The styrene derivative that can be used in the present invention is not particularly limited as long as living radical polymerization is possible, and can be appropriately selected according to the purpose. For example, those represented by the structural formula (1) are suitable.

  The core part in the hyperbranched polymer of the present invention is a homopolymer of the monomer represented by the above formula (1), or the monomer represented by the above formula (1) and the following formulas (2) to (5). More preferably, it is a copolymer with at least one selected monomer.

  In the core part of the hyperbranched polymer of the present invention, the constituent molar percentage of the monomer represented by the formula (1) is 5 to 100%, preferably 20 to 100%, more preferably 50 to 100%.

In said Formula (1), Y is a C1-C10 which may contain a hydroxyl group or a carboxyl group, Preferably it is C1-C8, More preferably, it is C1-C6 linear or branched. Or a cyclic alkylene group, for example, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, an amylene group, a hexylene group, a cyclohexylene group, etc. And -O-, -CO-, and -COO-. Among these, an alkylene group having 1 to 8 carbon atoms is preferable, a linear alkylene group having 1 to 8 carbon atoms is more preferable, and a methylene group, an ethylene group, an —OCH ₂ — group, and an —OCH ₂ CH ₂ — group are more preferable. .

  Z represents a halogen atom such as fluorine, chlorine, bromine or iodine. Among these, a chlorine atom and a bromine atom are preferable.

  Examples of the monomer represented by the formula (1) that can be used in the present invention include chloromethylstyrene, bromomethylstyrene, p- (1-chloroethyl) styrene, bromo (4-vinylphenyl) phenylmethane, and 1-bromo. -1- (4-vinylphenyl) propan-2-one, 3-bromo-3- (4-vinylphenyl) propanol, and the like. Of these, chloromethylstyrene, bromomethylstyrene, and p- (1-chloroethyl) styrene are preferable.

In the formula (2) ~ (5), R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Among these, a hydrogen atom and a methyl group are preferable. R ² and R ³ are each a hydrogen atom; a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms; or 6 to 30 carbon atoms. , Preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and R ² and R ³ may be the same or different from each other. Examples of linear, branched, and cyclic alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, cyclohexyl group, and the aryl group includes phenyl group. Group, 4-methylphenyl group, naphthyl group and the like. Among these, a hydrogen atom, a methyl group, an ethyl group, and a phenyl group are preferable.

R ⁴ is a hydrogen atom; a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms; a trialkylsilyl group (where each An alkyl group has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms; an oxoalkyl group (wherein the alkyl group has 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms); or the above formula (6 ), Wherein R ⁵ is a hydrogen atom; or a linear, branched, or cyclic carbon number of 1 to 10, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. Represents an alkyl group, R ⁶ and R ⁷ are each independently a hydrogen atom; or linear, branched or cyclic carbon atoms of 1 to 10, preferably 1 to 8 carbon atoms, more preferably 1 to carbon atoms. 6 alkyl groups or together to form a ring Representing the good).

In R ⁴ , the linear, branched or cyclic alkyl group includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, cycloheptyl. Group, triethylcarbyl group, 1-ethylnorbornyl group, 1-methylcyclohexyl group, adamantyl group, 2- (2-methyl) adamantyl group, tert-amyl group and the like.

In R ⁴ , examples of the trialkylsilyl group include those having 1 to 6 carbon atoms in each alkyl group such as a trimethylsilyl group, a triethylsilyl group, and a dimethyl-tert-butylsilyl group. Examples of the oxoalkyl group include a 3-oxocyclohexyl group.

  Examples of the group represented by the formula (6) include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxy. Ethyl group, 1-sec-butoxyethyl group, 1-tert-butoxyethyl group, 1-tert-amyloxyethyl group, 1-ethoxy-n-propyl group, 1-cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl Groups, linear or branched acetal groups such as 1-methoxy-1-methyl-ethyl group and 1-ethoxy-1-methyl-ethyl group; cyclic acetal groups such as tetrahydrofuranyl group and tetrahydropyranyl group, etc. Among these, ethoxyethyl group, butoxyethyl group, ethoxypropyl group, and tetrahydropyranyl group are particularly preferred. It is preferred.

  In the formula (5), n represents an integer of 0 to 10, preferably an integer of 0 to 7, more preferably an integer of 0 to 4.

As the monomer represented by the formula (2), in the formula (2), R ¹ is a hydrogen atom or a methyl group, and R ² and R ³ are each independently a hydrogen atom or a straight chain having 1 to 6 carbon atoms. Those that are chain or branched alkyl groups are preferred. Specific examples of the monomer represented by the formula (2) include styrene, α-methylstyrene, methylstyrene, dimethylstyrene, ethylstyrene, tert-butylstyrene, and phenylstyrene. Of these, styrene, α-methylstyrene, and methylstyrene are preferable.

As a monomer represented by the formula (3), in the formula (3), R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and R4 is Each of a hydrogen atom, or a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, or an alkyl group is represented by a trialkylsilyl group having 1 to 6 carbon atoms, or the above formula (6) (provided that R ⁵ is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, R ⁶ and R ⁷ are hydrogen atoms independent of each other, or a linear, branched or cyclic carbon number of 1 Those having an alkyl group of ˜6 or may be bonded to each other to form a ring) are preferred. Specific examples of the monomer represented by the formula (3) include hydroxystyrene, α-methylhydroxystyrene, methoxystyrene, tert-butoxystyrene, cyclohexyloxystyrene, trimethylsiloxystyrene, 4- (1-methoxyethoxy) styrene, 4- (1-ethoxyethoxy) styrene, tetrahydropyranyloxystyrene, etc. are mentioned. Of these, hydroxystyrene, methoxystyrene, tert-butoxystyrene, 4- (1-ethoxyethoxy) styrene, and tetrahydropyranyloxystyrene are preferable.

As the monomer represented by the formula (4), in the formula (4), R1 is a hydrogen atom or a methyl group, R4 is a hydrogen atom, or a linear, branched, or cyclic alkyl having 1 to 12 carbon atoms. Or a group represented by the formula (6) (wherein R ⁵ is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, R ⁶ and R ⁷ are hydrogen atoms independent of each other, or A linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or may be bonded to each other to form a ring is preferred. Specific examples of the monomer represented by the formula (4) include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, tert-butyl methacrylate, acrylic Examples thereof include adamantyl acid, adamantyl methacrylate, 2- (2-methyl) adamantyl acrylate, 2- (2-methyl) adamantyl methacrylate and the like. Among these, acrylic acid, methacrylic acid, tert-butyl acrylate, tert-butyl methacrylate, 2- (2-methyl) adamantyl acrylate, and 2- (2-methyl) adamantyl methacrylate are preferable.

  As a monomer represented by Formula (5), in Formula (5), R4 is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, and n is 1 to 5. Some are preferred. Specific examples of the monomer represented by the formula (5) include compounds represented by the following formulas (a1) to (g1). Of these, (a1), (d1), (e1), and (g1) are preferable.

  When the core part of the hyperbranched polymer of the present invention is a copolymer of the monomer represented by the formula (1) and at least one monomer selected from the formulas (2) to (5), the core part is constituted. The amount of the above formula (1) in all monomers is preferably 20 to 90 mol%, and more preferably 50 to 80 mol%. When the monomer represented by the formula (1) is contained in such an amount, the core portion is preferable because it takes a spherical shape advantageous for suppressing entanglement between molecules.

  The core portion of the hyperbranched polymer of the present invention is a living radical polymerized monomer represented by the formula (1), or at least one selected from the formula (1) and the formulas (2) to (5). It can synthesize | combine by carrying out a living radical polymerization reaction with the monomer of. Specifically, the core part of the hyperbranched polymer of the present invention can be produced by reacting the raw material monomers in a solvent such as chlorobenzene usually at 0 to 200 ° C. for 0.1 to 30 hours.

  The YZ bond in the monomer represented by the formula (1) is reversibly radically dissociated by the transition metal complex, and living radical polymerization proceeds by suppressing the bimolecular termination.

  For example, when chloromethylstyrene is used as the monomer represented by the formula (1) and a copper (I-valent) bipyridyl complex is used as a catalyst, the chloro atom in chloromethylstyrene converts the copper (I-valent) complex to copper (II-valent). In the oxidized state, an adduct is formed as an intermediate, and a methylene radical is generated on the side away from the chloro atom (see Jean MJ Frecht, J. Poly. Sci., 36, 955 (1998)). .

  This radical intermediate reacts with another ethylenic double bond of chloromethylstyrene to form a dimer represented by the following formula (9). At this time, since the primary carbon (1) and secondary carbon (2) generated in the molecule have a chloro group as a substituent, each of them reacts with another ethylenic double bond of chloromethylstyrene. To do. In the same manner, polymerization with chloromethylstyrene is successively caused.

  Moreover, in the tetramer represented by the following formula (10), the primary carbons (1) and (2), the secondary carbons (3) and (4) have a chloro group as a substituent, Each reacts with another ethylenic double bond of chloromethylstyrene. Thereafter, the reaction is repeated in the same manner to produce a highly branched polymer.

  At this time, if the amount of the copper complex serving as a catalyst is increased, the degree of branching further increases. Preferably, the amount of the catalyst is preferably 0.1 to 60 mol%, and preferably 1 to 40 mol%, based on the total amount of the monomer of the above formula (1) that forms the core portion. More preferably it is used. When the catalyst is used in such an amount, a hyperbranched polymer core portion having a suitable degree of branching described later can be obtained.

  The copolymer of the formula (1) and at least one monomer selected from the formulas (2) to (5) is transitioned by the same technique as the homopolymerization of the monomer represented by the formula (1). It can be produced by living radical polymerization using a metal complex.

  In addition, as monomers constituting the core portion of the hyperbranched polymer of the present invention, monomers other than those represented by the formulas (1) to (5) can be used as long as they have a structure having a radical polymerizable unsaturated bond. can do.

  Examples of the copolymerizable monomer that can be used include those shown below. For example, other than the above, styrenes and acrylic acid esters, methacrylic acid esters, and compounds having a radical polymerizable unsaturated bond selected from allyl compounds, vinyl ethers, vinyl esters and the like.

  Specific examples of styrenes include benzyl styrene, trifluoromethyl styrene, acetoxy styrene, chloro styrene, dichloro styrene, trichloro styrene, tetrachloro styrene, pentachloro styrene, bromo styrene, dibromo styrene, iodo styrene, fluoro styrene. , Trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, vinylnaphthalene and the like.

  Specific examples of acrylic esters include chloroethyl acrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane acrylate, glycidyl acrylate, acrylic acid Examples include benzyl, phenyl acrylate, and naphthyl acrylate.

  Specific examples of methacrylic acid esters include benzyl methacrylate, chlorobenzyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-methacrylate. Examples include hydroxypropyl, glycidyl methacrylate, phenyl methacrylate, naphthyl methacrylate, and the like.

  Specific examples of allyl esters include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, allyloxyethanol, and the like. .

  Specific examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxy Ethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl Ether, vinyl na Chirueteru, and vinyl anthranyl ether.

  Specific examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate. Vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate, and the like.

  Of these, styrenes are preferable, and benzylstyrene, chlorostyrene, and vinylnaphthalene are particularly preferable.

  In the hyperbranched polymer of the present invention, the constituent molar percentage of the monomer forming the core is 10 to 90%, preferably 20 to 80%, more preferably 30 to 70%. It is preferable that the constituent mole percent of the monomer constituting the core portion be in such a range because it has appropriate hydrophobicity with respect to the developer, and dissolution of unexposed portions is suppressed.

  When a monomer other than those represented by the above formulas (1) to (5) is used as the monomer constituting the core part, it is represented by the above formulas (1) to (5) in all monomers constituting the core part. The amount of the monomer to be formed is preferably 40 to 90 mol%, and more preferably 50 to 80 mol%. Use of the monomers represented by the above formulas (1) to (5) in such an amount is preferable because functions such as an increase in substrate adhesion and a glass transition temperature are imparted while maintaining the spherical shape of the core portion. . In addition, the quantity of the monomer represented by Formula (1)-(5) in a core part and another monomer can be adjusted with the preparation amount ratio at the time of superposition | polymerization according to the objective.

-Acid-decomposable group introduction step-
In the hyperbranched polymer of the present invention, the acid-decomposable group is introduced into the polymer end by reacting the core of the hyperbranched polymer that can be synthesized as described above with a compound containing the acid-decomposable group. be able to.

  In the present invention, the acid-decomposable group means a group that is decomposed by the action of an acid (preferably a photoacid generator that generates an acid by light energy). Groups that decompose to become hydrophilic groups are preferred. The acid-decomposable group is preferably selected from the group consisting of the following formulas (I) to (IV) and the following formula (7).

Here, R ^{1 ′} and R ^{2 ′} represent the same groups as described for R ¹ and R ² . Among these, a hydrogen atom and a linear alkyl group having 1 to 3 carbon atoms, particularly a hydrogen atom and a methyl group are preferable. R ⁸ is a hydrogen atom; a linear, branched or cyclic alkyl group having 3 to 40 carbon atoms, preferably 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms; a trialkylsilyl group (where each The alkyl group has 1 to 6 carbon atoms); an oxoalkyl group (wherein the alkyl group has 4 to 20 carbon atoms); or a group represented by the formula (6). Of these, a linear or branched alkyl group having 3 to 40 carbon atoms is preferable, and a tertiary alkyl group is particularly preferable.

In R ⁸ , a linear, branched or cyclic alkyl group (preferably a tertiary alkyl group) is a propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, cyclopentyl group, cyclohexyl group, Examples include cycloheptyl group, triethylcarbyl group, 1-ethylnorbornyl group, 1-methylcyclohexyl group, adamantyl group, 2- (2-methyl) adamantyl group, tert-amyl group and the like. Among these, a t-butyl group, 1-methylcyclohexyl group, adamantyl group, and 2- (2-methyl) adamantyl group are preferable.

In R ⁸ , examples of the trialkylsilyl group include those having 1 to 6 carbon atoms in each alkyl group such as a trimethylsilyl group, a triethylsilyl group, and a dimethyl-tert-butylsilyl group. Examples of the oxoalkyl group include a 3-oxocyclohexyl group.

R ⁹ and R ¹⁰ represent a hydrogen atom; a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms; or an aryl group having 6 to 30 carbon atoms, and R ⁹ and R ¹⁰ may be the same as each other They may be different and may form a ring together.

Examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms and the aryl group having 6 to 30 carbon atoms in R ⁹ and R ¹⁰ include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclopentyl group, 1-methylcyclopentyl group, cyclohexyl group, 1-methylcyclohexyl group, adamantyl group, triethylcarbyl group, 1-ethylnorbornyl Group, 1-methylcyclohexyl group, adamantyl group, 2- (2-methyl) adamantyl group, tert-amyl group, phenyl group, 2-methylphenyl group, 2-isopropylphenyl group, 2-t-butylphenyl group, phenyl A methyl group, 1-phenylethyl group, etc. are mentioned. Examples of R ⁹ and R ¹⁰ in which R ⁹ and R ¹⁰ together form a ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring. Among these, a methyl group, a phenyl group, a cyclopentane ring, a cyclohexane ring and the like are preferable.

  G is a halogen atom, a hydrogen atom, a cyano group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkylcarbonyloxy group (wherein the alkyl group Represents an alkyloxy group (wherein the alkyl group has 1 to 10 carbon atoms), a phenyloxy group, a thioether group, and an amino group. Among these, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonyloxy group, and a phenyloxy group, particularly a hydrogen atom, a chlorine atom, a bromine atom, a methylcarbonyloxy group, a phenyl group, and a phenyloxy group are preferable.

  In G, the halogen atom includes a chlorine atom and a bromine atom, and the alkyl group and aryl group include a methyl group, an ethyl group, a propyl group, a cyclohexyl group, an allyl group, a phenyl group, and the like. In G, the alkylcarbonyloxy group includes a methylcarbonyloxy group, an ethylcarbonyloxy group, and the like, and the thioether group includes a methylthioether group, an ethylthioether group, and a phenylthioether group. In G, examples of the amino group include a methylamino group, a dimethylamino group, a trimethylamino group, an ethylamino group, a diethylamino group, a triethylamino group, and a phenylamino group. Among these, a chlorine atom, a methyl group, a phenyl group, a methylcarbonyloxy group, a phenylthioether group, and a phenylamino group are preferable.

  In the unit (II), m represents an integer of 0 to 10, preferably an integer of 0 to 7, more preferably an integer of 0 to 4. In the units (I) to (IV), a, b, c and d are integers of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10.

  In formula (7), X represents an oxygen atom, a sulfur atom, a nitrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or an interatomic bond. Among these, an oxygen atom is preferable. W represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms; a phenyl group; an alkoxyphenyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or the following: The group represented by Formula (8) is shown. Of these, an alkoxyphenyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, and a group represented by the following formula (8) are preferable.

—R ¹¹ —COO—R ^{8 ′} formula (8)

In Formula (8), R ¹¹ is a linear, branched, or cyclic alkylene group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, or 6 to 6 carbon atoms. 30 represents an arylene group having preferably 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. R ¹¹ may contain an ether bond or an ester bond. R ^{8 ′} represents the same group as described above.

  In the formula (7), examples of the alkoxyphenyl group include t-butoxyphenyl group, p- (1-methoxyethoxy) phenyl group, p- (1-ethoxyethoxy) phenyl group, tetrahydrofuranyloxyphenyl group, tetrahydro Examples include a pyranyloxyphenyl group.

  In the formula (7), examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, a cyclohexylcarbonyl group, and a phenyloxycarbonyl group.

In the formula (8), as R ¹¹ , methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, cyclopentylene group, cyclohexylene group, phenylene group, naphthylene group, —C ₆ H ₄ OCH ₂ —, —C ₆ H ₈ OCH ₂ —, —C ₆ H ₅ O—, and the like.

  Therefore, the group represented by the formula (7) includes tert-butoxycarbonyloxy group, tert-butoxycarbonylmethyloxy group, p-tert-butoxycarbonylmethoxyphenyloxy group, tert-amyloxycarbonyloxy group, tert-amido. Examples include a loxycarbonylmethyloxy group, a 1-ethoxyethoxycarbonylmethyloxy group, a 2-tetrahydropyranyloxycarbonylmethyloxy group, a 2-tetrahydrofuranyloxycarbonylmethyloxy group, and the like. Among these, a tert-butoxycarbonylmethyloxy group and a p-tert-butoxycarbonylmethoxyphenyloxy group are preferable.

  Specific examples of the compound containing an acid-decomposable group include compounds represented by the following formulas (i) to (iv). Of these, compounds represented by formulas (i) and (iv) are preferred.

  Specific examples of the compound represented by formula (i) include tert-butyl acrylate, tert-butyl methacrylate, 1-methylcyclohexyl acrylate, 1-methylcyclohexyl methacrylate, adamantyl acrylate, adamantyl methacrylate, and acrylic. 2- (2-methyl) adamantyl acid, 2- (2-methyl) adamantyl methacrylate, triethylcarbyl acrylate, 1-ethylnorbornyl acrylate, 1-methylcyclohexyl acrylate, tetrahydropyranyl acrylate, methacrylic acid Examples include tetrahydropyranyl, trimethylsilyl acrylate, and dimethyl-tert-butylsilyl acrylate. Of these, tert-butyl acrylate, tert-butyl methacrylate, 2- (2-methyl) adamantyl acrylate, 2- (2-methyl) adamantyl methacrylate, tetrahydropyranyl acrylate, and tetrahydropyranyl methacrylate are preferred. .

  Specific examples of the compound represented by the formula (ii) include the structural formulas (d1) and (g1). Of these, (d1) and (g1) are preferable.

  Specific examples of the compound represented by the formula (iii) include compounds represented by the following formulas (15) to (17). Of these, (15) and (16) are preferable.

  Specific examples of the compound represented by the formula (iv) include tert.-butoxystyrene, α-methyl-tert-butoxystyrene, 4- (1-methoxyethoxy) styrene, 4- (1-ethoxyethoxy) styrene, Tetrahydropyranyloxystyrene, adamantyloxystyrene, 4- (2-methyl-2-adamantyloxy) styrene, 4- (1-methylcyclohexyloxy) styrene, trimethylsilyloxystyrene, dimethyl-tert-butylsilyloxystyrene, tetrahydropyrani Examples include ruoxystyrene. Of these, tert-butoxystyrene, 4- (1-ethoxyethoxy) styrene, tetrahydropyranyloxystyrene, and 4- (2-methyl-2-adamantyloxy) styrene are preferable.

  Monomers other than those represented by (I) to (IV) can also be used as acid-decomposable groups as long as they have a structure having a radical polymerizable unsaturated bond.

  Examples of the copolymerizable monomer that can be used include those shown below. For example, it is a compound having a radical polymerizable unsaturated bond selected from styrenes and acrylic esters other than the above, methacrylic ester, and allyl compounds, vinyl ethers, vinyl esters, crotonic acid esters, etc. .

  Specific examples of styrenes include benzyl styrene, trifluoromethyl styrene, acetoxy styrene, chloro styrene, dichloro styrene, trichloro styrene, tetrachloro styrene, pentachloro styrene, bromo styrene, dibromo styrene, iodo styrene, fluoro styrene. , Trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, vinylnaphthalene and the like.

  Specific examples of acrylic esters include chloroethyl acrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane acrylate, glycidyl acrylate, acrylic acid Examples include benzyl, phenyl acrylate, and naphthyl acrylate.

  Specific examples of methacrylic acid esters include benzyl methacrylate, chlorobenzyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-methacrylate. Examples include hydroxypropyl, glycidyl methacrylate, phenyl methacrylate, naphthyl methacrylate, and the like.

  Specific examples of allyl esters include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, allyloxyethanol, and the like. .

  Specific examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, Hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichloro Phenyl ether, vinyl Naphthyl ether, and vinyl anthranyl ether.

  Specific examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate. Vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate, and the like.

  Specific examples of crotonic acid esters include butyl crotonate, hexyl crotonate, glycerol monocrotonate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, dimethyl maleate, dibutyl fumarate, maleic anhydride, maleimide, acrylonitrile , Methacrylonitrile, maleilonitrile and the like.

  Of these, styrenes, acrylic acid esters, methacrylic acid esters, and crotonic acid esters are preferable. Among them, benzylstyrene, chlorostyrene, vinyl naphthalene, benzyl acrylate, phenyl acrylate, naphthyl acrylate, benzyl methacrylate, methacrylic acid, and the like. Preference is given to phenyl acid, naphthyl methacrylate, butyl crotonate, hexyl crotonate and maleic anhydride.

  In the hyperbranched polymer of the present invention, the constituent molar percentage of at least one repeating unit selected from the above formulas (I) to (IV) that form an acid-decomposable group is 10 to 90%, preferably 20 to 80%. More preferably, 30 to 70% is suitable. Within such a range, the exposed area is efficiently dissolved and removed in the alkaline solution in the development step, which is preferable.

  In the hyperbranched polymer of the present invention, the constituent mole percent of the group represented by the formula (7) that forms the acid-decomposable group is 10 to 50%, preferably 20 to 50%, more preferably 30 to 50%. Is preferred. Within such a range, the exposed area is efficiently dissolved and removed in the alkaline solution in the development step, which is preferable.

  When using monomers other than those represented by the above formulas (I) to (IV) and formula (7) as the acid decomposable group, the above formula ( The repeating units represented by I) to (IV) and formula (7) are preferably 30 to 90 mol%, more preferably 50 to 70 mol%. Within such a range, functions such as etching resistance, wettability, and increase in glass transition temperature are imparted without hindering efficient alkali solubility in the exposed area. In addition, the amount of the repeating unit represented by the formulas (I) to (IV) and the formula (7) in all the acid-decomposable groups and the other repeating units depends on the charged amount ratio at the time of introducing the core part depending on the purpose. Can be adjusted.

  The acid-decomposable group can be introduced by either one of the following two methods or a combination thereof.

<First method>
The first method is a method in which the acid-decomposable groups represented by (I) to (IV) can be introduced using the above formulas (i) to (iv) as compounds containing an acid-decomposable group. is there.

  As the catalyst, a transition metal complex catalyst similar to the catalyst used for the synthesis of the core portion of the hyperbranched polymer, for example, a copper (I) bipyridyl complex, is used, and the starting point is a halogenated carbon present at the terminal of the core portion. As described above, linear addition polymerization is performed by living radical polymerization with a double bond of at least one compound represented by the above formulas (i) to (iv). Specifically, the core part and at least one compound represented by the above formulas (i) to (iv) are usually added in a solvent such as chlorobenzene at 0 to 200 ° C. for 0.1 to 30 hours. By reacting, the acid-decomposable groups represented by (I) to (IV) can be introduced to produce the hyperbranched polymer of the present invention.

  As an example, the reaction formula for introducing an acid-decomposable group into the core of a hyperbranched polymer formed from chloromethylstyrene is shown in Reaction Formula 1. In the groups represented by (I) to (IV), the group represented by G can introduce the introduced acid-decomposable group by a known reaction for halogenated carbon.

<Second method>
The second method is AXW in the following reaction formula 2 as a compound containing an acid-decomposable group (where A can generate anion species, cation species, and radical species on X by elimination of A). The acid-decomposable group represented by the formula (7) can be introduced. Specifically, it is represented by the formula (7) by reacting the core with AXW in a solvent such as chlorobenzene usually at −78 to 150 ° C. for 0.5 to 30 hours. The hyperbranched polymer of the present invention can be produced by introducing an acid-decomposable group. What is necessary is just to introduce | transduce by the well-known reaction with respect to the halogenated carbon by making the halogenated carbon which exists many in the terminal of the synthesized core part into a reaction point. For example, by the following substitution reaction of the chloro group present at the end of the core synthesized from chloromethylstyrene and the X-W group.

        Reaction Formula 2 -C-Cl + AXW → -CXW

  In Reaction Scheme 2, A is a group capable of generating an anionic species, a cationic species, and a radical species on X by the elimination of A.

  The hyperbranched polymer is a group consisting of a homopolymer of the monomer represented by the formula (1) or the monomer represented by the formula (1) and the monomer represented by the formulas (2) to (5). It is preferably composed of a core part which is a copolymer of at least one selected and an acid-decomposable group represented by the formula (I), (II), (III) or (7).

  The hyperbranched polymer is a homopolymer of the monomer represented by the formula (1) or the group represented by the monomer represented by the formula (1) and the monomer represented by the formulas (2) to (4). It is also preferable that it is composed of a core part which is a copolymer with at least one kind selected, and an acid-decomposable group represented by the formula (I), (III) or (IV).

  The hyperbranched polymer is a copolymer of at least one selected from the group consisting of monomers represented by the formula (2), (4) or (5), and the formula (IV) It is also preferable that it is comprised from the acid-decomposable group represented.

  The introduction ratio of the acid-decomposable group in the hyperbranched polymer of the present invention is preferably 0.05 or more, more preferably 0, with respect to the number of monomers represented by the formula (1) constituting the core portion of the hyperbranched polymer. 0.1 or more, more preferably 0.15 or more, more preferably 0.2 or more, further preferably 0.3 or more, more preferably 0.5 or more, more preferably 0.6 or more, preferably 20 In the following, it is more preferably 15 or less, further preferably 10 or less, further preferably 7 or less, and further preferably 5 or less. Preferably it is 0.05-20, More preferably, it is 0.1-20, More preferably, it is 0.3-20, More preferably, it is 0.3-15, More preferably, it is 0.5-10, Most preferably, it is 0.6 ~ 5. Within such a range, it is preferable in the development process because the exposed portion is efficiently removed by alkali dissolution and the unexposed portion is prevented from dissolving, which is advantageous for fine pattern formation.

  In the hyperbranched polymer of the present invention, the acid-decomposable group constituting the hyperbranched polymer is converted into an acidic group such as a carboxyl group or a phenolic hydroxyl group by a partial decomposition reaction using a catalyst after being introduced into the core part. May be.

  Specific examples of the catalyst include acid catalysts such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, paratoluenesulfonic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, formic acid, or sodium hydroxide, potassium hydroxide. An alkali catalyst such as An acid catalyst is preferable, and hydrochloric acid, paratoluenesulfonic acid, acetic acid, trifluoroacetic acid, and formic acid are preferable.

In at least one repeating unit selected from the above formulas (I) to (IV) that form an acid-decomposable group, the constituent moles of the repeating unit having an acidic group in which R ⁸ in the hyperbranched polymer of the present invention is a hydrogen atom. The percentage is suitably 0 to 70%, preferably 0 to 60%, more preferably 0 to 50%. Within such a range, it is advantageous because it is advantageous for increasing the sensitivity of the resist in the exposure process.

In the above formula (7) for forming an acid-decomposable group, the constituent molar percentage of the group in which R ⁸ is a hydrogen atom in the hyperbranched polymer of the present invention is 0 to 40%, preferably 0 to 30%, more preferably 0 to 20% is preferable. If it is in such a range, it is advantageous for improving the sensitivity of the resist without alienating the suppression of dissolution of the unexposed area.

Here, the introduction ratio of the acid-decomposable group is determined by measuring the ¹ H-NMR of the product, and the integral value of protons characteristic of the acid-decomposable group in terms of moles relative to the monomer represented by the formula (1). It can be calculated as a ratio or using any of the following mathematical formulas (a) to (c).

R: for the monomer represented by Formula 1 constituting the core portion,
Introduction molar ratio of acid-decomposable group Am: Average molecular weight of monomer having acid-decomposable group Bm: Average molecular weight of molecule having dehalogenated acid-decomposable group Cm: Monomer represented by formula 1 constituting the core portion Average molecular weight of Dm: Monomer other than Formula 1 constituting the core portion and having no acid-decomposable group
Average molecular weight of Em: Average molecular weight of the monomer constituting the core portion and having an acid-decomposable group AW: Weight average molecular weight of the hyperbranched polymer into which the acid-decomposable group was introduced BW: of the debranched hyperbranched polymer Weight average molecular weight CW: Weight average molecular weight of the core portion X: Atomic weight of halogen present in the monomer constituting the core portion r: Mol% of the monomer represented by Formula 1 constituting the core portion
s: mol% of the monomer constituting the core portion and having an acid-decomposable group

  The branching degree (Br) of the core part in the hyperbranched polymer is preferably 0.1 to 0.9, more preferably 0.3 to 0.7, and 0.4 to 0.5. More preferably, it is most preferably 0.5. When the degree of branching of the core is in such a range, it is preferable because entanglement between polymer molecules is small and surface roughness on the pattern side wall is suppressed.

Here, the degree of branching can be determined as follows by measuring ¹ H-NMR of the product. That is, the calculation was performed according to the following formula (A) using the integral ratio H1 ° of protons at —CH ₂ Cl sites appearing at 4.6 ppm and the integral ratio H2 ° of protons at CHCl sites appearing at 4.8 ppm. When the polymerization proceeds at both the —CH ₂ Cl site and the CHCl site and branching increases, the Br value approaches 0.5.

  The weight average molecular weight of the core part in the hyperbranched polymer of the present invention is preferably 300 to 100,000, more preferably 500 to 80,000, and more preferably 1,000 to 100,000. Preferably, it is 1,000 to 50,000, more preferably 5,000 to 50,000. When the molecular weight of the core part is in such a range, the core part takes a spherical shape and is preferable because it can ensure solubility in the reaction solvent in the acid-decomposable group introduction reaction. Furthermore, it is preferable to use a hyperbranched polymer that is excellent in film formability and has an acid-decomposable group derived in the core part within the above molecular weight range because it is advantageous for inhibiting dissolution of the unexposed part.

  The weight average molecular weight (Mw) of the hyperbranched polymer of the present invention is preferably 500 to 150,000, more preferably 2,000 to 150,000, still more preferably 1,000 to 100,000, still more preferably 2, 000-60,000, most preferably 6,000-60,000. The resist containing a hyperbranched polymer having a weight average molecular weight of less than 500 may have poor film formability and cannot be coated on the substrate, or the processing pattern formed in the lithography process may not be strong enough to maintain its shape. In the etching process, the etching resistance may be lowered. If the weight average molecular weight is less than 2,000, the strength of the processed pattern may be low and the shape may not be maintained. If the weight average molecular weight exceeds 150,000, the size of the polymer molecule may adversely affect the surface roughness. .

  Here, the weight average molecular weight (Mw) can be determined by preparing a 0.05 wt% tetrahydrofuran solution and performing GPC measurement at a temperature of 40 ° C. Tetrahydrofuran can be used as the mobile solvent, and styrene can be used as the standard substance.

When the hyperbranched polymer of the present invention is synthesized using a transition metal complex as a catalyst, the resulting hyperbranched polymer may contain a transition metal. The amount depends on the type and amount of the catalyst used, but can usually be contained in the hyperbranched polymer in an amount of 5 to 7 ppm. At this time, it is preferable to remove the catalyst-derived metal contained in the hyperbranched polymer of the present invention until the amount thereof is less than 100 ppb, preferably less than 80 ppb, more preferably less than 60 ppb. When the amount of the metal derived from the catalyst is 100 ppb or more, the irradiation light is absorbed by the mixed metal element in the exposure process, the resist sensitivity is lowered, and the throughput may be adversely affected. Further, in the process of removing the dry-etched resist by dry ashing using O ₂ plasma or the like, a mixed metal element may adhere or diffuse on the substrate by the plasma, and various adverse effects may be caused in the subsequent process. The amount of metal element can be measured by ICPMAS (for example, P-6000 type MIP-MS manufactured by Hitachi, Ltd.). As a means for removal, for example, an ion exchange membrane (for example, Protego CP, manufactured by Nihon Microlith Co., Ltd.) and a membrane membrane (for example, manufactured by Millipore, Millipore filter) are used alone or in combination. Means are mentioned. For example, when the flow rate of the polymer solution is adjusted to 0.5 to 10 ml / min, the metal element removal effect is advantageously affected, which is preferable.

The solubility of the hyperbranched polymer of the present invention in an alkaline aqueous solution is, for example, 50 to 5000 mJ / cm in a predetermined size portion with respect to a sample thin film having a predetermined thickness formed on a silicon wafer using an electron beam drawing apparatus. ^{2 with} an electron beam of ² or with a discharge tube type ultraviolet irradiation device, a sample thin film having a predetermined thickness formed on a silicon wafer, with a wavelength of 245 nm energy of 0 to 200 mJ / cm ^{2 in} a predetermined size portion Evaluate by irradiating with ultraviolet rays, immersing in alkaline aqueous solution after heat treatment, observing the state after water washing and drying with a digital microscope, or measuring the film thickness after water washing and drying with a thin film measuring device can do.

  The surface roughness of the exposed surface is, for example, the method described in Masao Nagase, Waseda University Review Thesis 2475, “Study on Nanostructure Measurement by Atomic Force Microscope and its Application to Devices and Processes”, pp99-107 (1996). Can be measured according to. Specifically, an electron beam drawing apparatus or a discharge tube type ultraviolet irradiation apparatus can be used for the surface of 30% of the exposure amount of the electron beam or the ultraviolet light exposure that showed solubility in the alkaline aqueous solution. For an evaluation sample prepared in the same manner as described for the solubility in an alkaline aqueous solution, measured using an atomic force microscope according to the ten-point average roughness of JIS B0601-1994, which is an index of surface roughness. it can.

  The hyperbranched polymer of the present invention obtained by the method for producing a hyperbranched polymer of the present invention has an advanced branch (branch) structure in the core portion, so that the entanglement between molecules seen in a linear polymer is small, and Compared with the molecular structure that crosslinks the main chain, the swelling by the solvent is also small, and therefore the formation of large molecular aggregates that cause surface roughness is suppressed. In addition, since the hyperbranched polymer of the present invention has an acid-decomposable group at the molecular end, in photolithography, a decomposition reaction occurs due to the action of an acid generated from the photoacid generator at the exposed portion, resulting in a hydrophilic group. As a result, it can take a micellar structure having a large number of hydrophilic groups on the outer periphery of the molecule, can be efficiently dissolved in an alkaline aqueous solution, and can form a fine pattern. The base resin of the following resist composition Can be suitably used.

(Resist composition)
The resist composition of the present invention comprises at least the hyperbranched polymer of the present invention, a photoacid generator, and, if necessary, an acid diffusion inhibitor (acid scavenger), a surfactant, other components, and a solvent. Can be included.

  The compounding amount of the hyperbranched polymer of the present invention is preferably 4 to 40% by weight, more preferably 4 to 20% by weight, based on the total amount of the resist composition.

  The photoacid generator is not particularly limited as long as it generates an acid upon irradiation with ultraviolet rays, X-rays, electron beams, and the like, and can be appropriately selected from known ones according to the purpose. Examples include onium salts, sulfonium salts, halogen-containing triazine compounds, sulfone compounds, sulfonate compounds, aromatic sulfonate compounds, and sulfonate compounds of N-hydroxyimide.

  Examples of the onium salt include diaryl iodonium salts, triaryl selenonium salts, and triaryl sulfonium salts. Examples of the diaryliodonium salt include diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium hexafluoroantimonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, Examples thereof include bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluoroantimonate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, and the like. Examples of the triarylselenonium salt include triphenylselenonium hexafluorophosphonium salt, triphenylselenonium borofluoride, triphenylselenonium hexafluoroantimonate salt, and the like. Examples of the triarylsulfonium salt include triphenylsulfonium hexafluorophosphonium salt, triphenylsulfonium hexafluoroantimonate salt, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate salt, diphenyl-4-thiophenoxyphenylsulfonium penta Fluorohydroxyantimonate salts and the like.

  Examples of the sulfonium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium hexafluoroantimonate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate. , P-tolyldiphenylsulfonium trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphate, 4-phenylthiophene Nyldiphenylsulfonium hexafluoroantimonate, 1- (2-naphthoylmethyl) thiolanium hexafluoroantimonate, 1- (2-naphthoylmethyl) thiolanium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium hexafluoro Antimonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, and the like.

  Examples of the halogen-containing triazine compound include 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6-tris (trichloromethyl) -1,3,5- Triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxy-1-naphthyl) -4,6-bis (trichloromethyl) -1 , 3,5-triazine, 2- (benzo [d] [1,3] dioxolan-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxy) Styryl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- ( 3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3 , 5-triazine, 2- (2-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-butoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-pentyloxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and the like.

  Examples of the sulfone compound include diphenyldisulfone, di-p-tolyldisulfone, bis (phenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, and bis (4-tert-butyl). Phenylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, (benzoyl) (phenylsulfonyl) diazomethane, phenylsulfonylacetophenone, and the like.

  Examples of the aromatic sulfonate compound include α-benzoylbenzyl p-toluenesulfonate (common name: benzoin tosylate), β-benzoyl-β-hydroxyphenethyl p-toluenesulfonate (common name: α-methylol benzoin tosylate), 1,2 , 3-Benzenetriyltrismethanesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2-nitrobenzyl p-toluenesulfonate, 4-nitrobenzyl p-toluenesulfonate, and the like.

  Examples of the sulfonate compound of N-hydroxyimide include N- (phenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) succinimide, N- (p-chlorophenylsulfonyloxy) succinimide, N- (cyclohexylsulfonyloxy). ) Succinimide, N- (1-naphthylsulfonyloxy) succinimide, N- (benzylsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoro Methylsulfonyloxy) -5-norbornene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthalimide, N- (10-camphorsulfur Niruokishi) naphthalimide, and the like.

  The photoacid generator is preferably a sulfonium salt, particularly triphenylsulfonium trifluoromethanesulfonate; a sulfone compound, particularly bis (4-tert-butylphenylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane.

  The photoacid generators can be used alone or in admixture of two or more. The blending amount of the photoacid generator is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the hyperbranched polymer of the present invention, 0.1-10 weight part is more preferable.

  Further, the acid diffusion inhibitor is not particularly limited as long as it is a component having an action of controlling an undesired chemical reaction in a non-exposed region by controlling a diffusion phenomenon in the resist film of an acid generated from an acid generator by exposure. And can be appropriately selected from known ones according to the purpose. For example, a nitrogen-containing compound having one nitrogen atom in the same molecule, a compound having two nitrogen atoms in the same molecule, 3 nitrogen atoms Examples thereof include polyamino compounds and polymers having at least one compound, amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds.

  Examples of the nitrogen-containing compound having one nitrogen atom in the same molecule include mono (cyclo) alkylamine, di (cyclo) alkylamine, tri (cyclo) alkylamine, and aromatic amine. Examples of the mono (cyclo) alkylamine include n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, and cyclohexylamine. Examples of the di (cyclo) alkylamine include di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, and di-n-. Nonylamine, di-n-decylamine, cyclohexylmethylamine, and the like. Examples of the tri (cyclo) alkylamine include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n- Examples include octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, tricyclohexylamine, and the like. Examples of the aromatic amine include aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, and naphthylamine. , Etc.

  Examples of the nitrogen-containing compound having two nitrogen atoms in the same molecule include ethylenediamine, N, N, N′N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4 -Aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [ 1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-amino Phenyl) -1-methylethyl] benzene, bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether, and the like.

  Examples of the polyamino compound or polymer having 3 or more nitrogen atoms include polyethyleneimine, polyallylamine, N- (2-dimethylaminoethyl) acrylamide polymer, and the like.

  Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt -Butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′-diaminodiphenylmethane, N, N′-di-t-butoxycarbonylhexamethylenediamine, N, N, N′N′-tetra-t-butoxycarbonylhexamethyl Diamine, N, N′-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t-butoxy Carbonyl-1,9-diaminononane, N, N′-di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12-diaminododecane, N, N ′ -Di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole , Formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylamide Toamido, N, N- dimethylacetamide, propionamide, benzamide, pyrrolidone, N- methylpyrrolidone, and the like.

  Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butyl. And thiourea.

  Examples of the nitrogen-containing heterocyclic compound include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, pyridine, 2-methylpyridine, 4-methylpyridine, 2- Ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, Piperazine, 1- (2-hydroxyethyl) piperazine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1,4-dimethylpi Rajin, 1,4-diazabicyclo [2.2.2] octane, and the like.

  The acid diffusion inhibitors can be used alone or in admixture of two or more. There is no restriction | limiting in particular as a compounding quantity of the said acid diffusion inhibitor, Although it can select suitably according to the objective, 0.1-1000 weight part is preferable with respect to 100 weight part of said photoacid generators, and 0.0. 5-10 weight part is more preferable.

  The surfactant is not particularly limited as long as it is a component that exhibits an effect of improving coatability, striation, developability, etc., and can be appropriately selected from known ones according to the purpose. , Polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, sorbitan fatty acid ester, nonionic surfactant of polyoxyethylene sorbitan fatty acid ester, fluorine-based surfactant, silicon-based surfactant, and the like.

  Examples of the polyoxyethylene alkyl ether include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and the like. Examples of the polyoxyethylene alkyl allyl ether include polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether. Examples of the sorbitan fatty acid ester include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, and the like. Examples of the nonionic surfactant of the polyoxyethylene sorbitan fatty acid ester include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate. , Polyoxyethylene sorbitan tristearate, and the like. Examples of the fluorine-based surfactant include F-top EF301, EF303, and EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFuck F171, F173, F176, F189, and R08 (manufactured by Dainippon Ink & Chemicals, Inc.) , FLORAD FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), and the like. Examples of the silicon surfactant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

  The surfactants can be used alone or in admixture of two or more. The blending amount of the surfactant is not particularly limited and may be appropriately selected according to the purpose. However, 0.0001 to 5 parts by weight is preferable with respect to 100 parts by weight of the hyperbranched polymer of the present invention, 0.0002 to 2 parts by weight is more preferable.

  Examples of the other components include a sensitizer, a dissolution controller, an additive having an acid dissociable group, an alkali-soluble resin, a dye, a pigment, an adhesion aid, an antifoaming agent, a stabilizer, an antihalation agent, and the like. Is mentioned.

  As the sensitizer, it absorbs radiation energy and transmits the energy to the photoacid generator, thereby increasing the amount of acid generated, and improving the apparent sensitivity of the resist composition. As long as it has, there is no particular limitation, and examples thereof include acetophenones, benzophenones, naphthalenes, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines, and the like. These sensitizers can be used alone or in admixture of two or more.

  The dissolution control agent is not particularly limited as long as it can more appropriately control the dissolution contrast and dissolution rate when used as a resist, and examples thereof include polyketones and polyspiroketals. These dissolution control agents can be used alone or in admixture of two or more.

  The additive having an acid-dissociable group is not particularly limited as long as it further improves dry etching resistance, pattern shape, adhesion to a substrate, and the like. For example, 1-adamantane carboxylate t-butyl, -T-butoxycarbonylmethyl adamantanecarboxylate, di-t-butyl 1,3-adamantane dicarboxylate, t-butyl 1-adamantane acetate, t-butoxycarbonylmethyl 1-adamantane acetate, di- 1,3-adamantane diacetate t-butyl, deoxycholic acid t-butyl, deoxycholic acid t-butoxycarbonylmethyl, deoxycholic acid 2-ethoxyethyl, deoxycholic acid 2-cyclohexyloxyethyl, deoxycholic acid 3-oxocyclohexyl, deoxycholic acid tetrahydropyrani Le, deoxycholate meba Nolactone ester, t-butyl lithocholic acid, t-butoxycarbonylmethyl lithocholic acid, 2-ethoxyethyl lithocholic acid, 2-cyclohexyloxyethyl lithocholic acid, 3-oxocyclohexyl lithocholic acid, tetrahydropyranyl lithocholic acid, mevalono lithocholic acid Lactone esters, and the like. These dissolution control agents can be used alone or in admixture of two or more.

  The alkali-soluble resin is not particularly limited as long as it improves the alkali-solubility of the resist composition of the present invention. For example, poly (4-hydroxystyrene), partially hydrogenated poly (4-hydroxystyrene), poly (3-hydroxystyrene), poly (3-hydroxystyrene), 4-hydroxystyrene / 3-hydroxystyrene copolymer, 4-hydroxystyrene / styrene copolymer, novolac resin, polyvinyl alcohol, polyacrylic acid and the like. Mw is usually from 1,000 to 1,000,000, preferably from 2,000 to 100,000. These alkali-soluble resins can be used alone or in admixture of two or more.

  The dye or the pigment can visualize the latent image in the exposed area and can reduce the influence of halation during exposure. In addition, the adhesion aid can improve the adhesion to the substrate.

  The solvent is not particularly limited as long as it can dissolve the components and the like, and can be appropriately selected from those that can be safely used in resist compositions. For example, ketone, cyclic ketone, propylene glycol monoalkyl Examples include ether acetate, alkyl 2-hydroxypropionate, alkyl 3-alkoxypropionate, and other solvents.

  Examples of the ketone include methyl isobutyl ketone, methyl ethyl ketone, 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3 , 3-dimethyl-2-butanone, 2-heptanone, 2-octanone, and the like. Examples of the cyclic ketone include cyclohexanone, cyclopentanone, 3-methylcyclopentanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, and isophorone. Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n. -Butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol mono-t-butyl ether acetate, and the like. Examples of the alkyl 2-hydroxypropionate include methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate, i-propyl 2-hydroxypropionate, and n-hydroxypropionate n. -Butyl, i-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate, t-butyl 2-hydroxypropionate, and the like. Examples of the alkyl 3-alkoxypropionate include methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and the like.

  Examples of the other solvent include n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl. Ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n -Propyl ether acetate, propylene glycol, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3 -Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate , Methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzyl ethyl ether, di-n-hexyl ether, diethylene glyco Rumonomethyl ether, diethylene glycol monoethyl ether, γ-butyrolactone, toluene, xylene, caproic acid, caprylic acid, octane, decane, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, malein Examples include diethyl acid, ethylene carbonate, and propylene carbonate. These solvents can be used alone or in admixture of two or more.

  The resist composition of the present invention can be subjected to patterning by developing after being exposed in a pattern. The resist composition of the present invention can be applied to electron beams, deep ultraviolet (DUV), and extreme ultraviolet (EUV) light sources whose surface smoothness is required on the nano order, and can form fine patterns for the production of VLSI. It can be suitably used in the field. The resist composition of the present invention can be dissolved in an alkali developer by exposure and heating, washed with water, etc., so that almost no undissolved residue is left on the exposed surface, and a substantially vertical edge can be obtained.

Example 1A
-Synthesis of hyperbranched polymer-
In a 50 mL reaction vessel, 21 mmol of chloromethylstyrene as a reaction monomer, 2.1 mmol of 2,2-bipyridyl as a catalyst, 1.1 mmol of copper (I) chloride, and 8 mL of chlorobenzene as a solvent were accommodated. After substituting with argon, the mixture was stirred at a temperature of 115 ° C. and polymerized for 1 hour. Tetrahydrofuran 50mL was added to this reaction liquid, the polymer was diluted and dissolved, and then the catalyst was removed by activated alumina filtration. After concentration of the filtrate, 200 mL of methanol was added to precipitate the polymer, and the unreacted monomer and the reaction solvent were removed by removing the supernatant. Next, the precipitated polymer was dissolved in 20 mL of tetrahydrofuran, 500 mL of methanol was added, and reprecipitation was repeated twice to synthesize polymer 1 (yield 75%). The above is the hyperbranched polymer synthesis step.
About the obtained polymer 1, the weight average molecular weight (Mw) and the branching degree (Br) were measured as follows. The results are shown in Table 1A.

<Measurement of weight average molecular weight (Mw)>
The weight average molecular weight (Mw) of the hyperbranched polymer was determined by preparing a 0.05 mass% tetrahydrofuran solution and performing GPC measurement at a temperature of 40 ° C. Tetrahydrofuran was used as the mobile solvent. Styrene was used as a standard substance.

<Degree of branching>
The degree of branching of the hyperbranched polymer was determined as follows by measuring ¹ H-NMR of the product. That is, the calculation was performed according to the following formula (A) using the integral ratio H1 ° of protons at —CH ₂ Cl sites appearing at 4.6 ppm and the integral ratio H2 ° of protons at CHCl sites appearing at 4.8 ppm. When the polymerization proceeds at both the —CH ₂ Cl site and the CHCl site and branching increases, the Br value approaches 0.5.

  Next, 1 g of the polymer 1 as a raw material polymer, 6.5 mmol of p-tert-butoxystyrene as a compound containing an acid-decomposable group, and 2,2-bipyridyl as a catalyst in a 50 mL reaction vessel. 2 mmol, 1.6 mmol of copper (I) chloride, and 8 mL of chlorobenzene as a solvent were accommodated, and the inside of the reaction vessel was purged with argon, followed by stirring at a temperature of 125 ° C. for polymerization for 30 minutes. Tetrahydrofuran 50mL was added to this reaction liquid, the polymer was diluted and dissolved, and then the catalyst was removed by activated alumina filtration. After concentration of the filtrate, 200 mL of methanol was added to precipitate the polymer, and the supernatant was removed to remove unreacted monomers and reaction solvent. Next, the precipitated polymer was dissolved in 20 mL of tetrahydrofuran, 500 mL of methanol was added, and reprecipitation was repeated twice to synthesize a hyperbranched polymer into which the target acid-decomposable group represented by the following formula was introduced. The above is the acid-decomposable group introduction step.

  The addition amount (introduction amount) of the acid-decomposable group in the obtained hyperbranched polymer into which the acid-decomposable group was introduced was measured as follows. The results are shown in Table 1A.

<Addition amount of acid-decomposable group (introduction amount)>
The amount of the acid-decomposable group added was determined by measuring the ¹ H-NMR of the product and calculating the ratio of the integral value of protons characteristic of the acid-decomposable group to the number of styrene derivatives that are constituent units of the hyperbranched polymer. .

(Example 2A)
-Synthesis of hyperbranched polymer-
In Example 1, Polymer 2 was synthesized in the same manner as in Example 1 except that the amount of catalyst in the hyperbranched polymer synthesis step was 5 times, the polymerization was performed at a reaction temperature of 125 ° C. and a reaction time of 30 minutes. (Yield 77%). In the same manner as in Example 1, the weight average molecular weight (Mw) and the degree of branching (Br) of the polymer 2 were measured. The results are shown in Table 1A.

  Example 1 except that 1 g of polymer 2 as a raw material polymer in the acid-decomposable group introduction step, 65 mmol of p-tert-butoxystyrene as a compound containing an acid-decomposable group, and 3 hours of reaction time were used. In the same manner as above, polymerization with p-tert-butoxystyrene and purification were carried out to synthesize a hyperbranched polymer into which the target acid-decomposable group was introduced. In the same manner as in Example 1, the addition amount (introduction amount) of the acid-decomposable group was measured. The results are shown in Table 1A.

(Example 3A)
-Synthesis of hyperbranched polymer-
In Example 1, polymer 3 was synthesized in the same manner as in Example 1 except that the amount of catalyst in the hyperbranched polymer synthesis step was 4 times, the reaction temperature was 125 ° C., and the reaction time was 1 hour (yield) 78%). In the same manner as in Example 1, the weight average molecular weight (Mw) and the degree of branching (Br) of the polymer 3 were measured. The results are shown in Table 1A.

  Example 1 except that 1 g of polymer 3 as a raw material polymer in the acid-decomposable group introduction step, 65 mmol of p-ethoxyethoxystyrene as a compound containing an acid-decomposable group, and 3 hours of reaction time were used. Similarly, polymerization with p-ethoxyethoxystyrene and purification were performed to synthesize a hyperbranched polymer into which the target acid-decomposable group was introduced. In the same manner as in Example 1, the addition amount (introduction amount) of the acid-decomposable group was measured. The results are shown in Table 1A.

(Example 4A)
In a 50 mL reaction vessel, 1 g of polymer 3 as a starting polymer, 13.0 mmol of hydroquinone tert-butyl ether as a compound containing an acid-decomposable group, and 13.0 mmol of NaH were accommodated, and 30 mL of tetrahydrofuran was added as a solvent. The reaction was carried out at 70 ° C. under reflux for 5 hours. 200 mL of methanol was added to the reaction product, and the precipitated polymer was separated by decantation, washed with water, and dried to synthesize a hyperbranched polymer into which the target acid-decomposable group represented by the following formula was introduced. The above is the acid-decomposable group introduction step. In the same manner as in Example 1, the addition amount (introduction amount) of the acid-decomposable group was measured. The results are shown in Table 1A.

(Example 5A)
In Example 4, except that 65 mmol of 4-hydroxyphenyloxyacetic acid tert-butyl ester as a compound containing an acid-decomposable group in the acid-decomposable group introduction step and a reaction time of 3 hours were used. In the same manner as above, reaction with 4-hydroxyphenyloxyacetic acid tert-butyl ester and purification were carried out to synthesize a hyperbranched polymer into which the target acid-decomposable group was introduced. In the same manner as in Example 1, the addition amount (introduction amount) of the acid-decomposable group was measured. The results are shown in Table 1A.

(Examples 6A to 10A)
-Preparation of resist composition-
Table 1A shows 10% by mass of each hyperbranched polymer having an acid-decomposable group introduced in Examples 1 to 5 and a propylene glycol monomethyl acetate solution containing 0.1% by mass of a photoacid generator (PAG1 to 3). The resist compositions of Examples 6 to 10 were prepared by mixing in the combinations shown. Each of the obtained resist compositions was spin-coated on a silicon wafer, and the solvent was evaporated by a heat treatment at 90 ° C. for 1 minute to produce a thin film having a thickness of 300 nm, which was used as an evaluation sample.

<Alkali-soluble evaluation method>
The solubility in an alkaline aqueous solution is 50 in a square portion of 30 μm in length and 30 μm in width with respect to a sample thin film having a thickness of about 300 nm formed on a silicon wafer by using an electron beam drawing apparatus (CRESTEC, CABL9000). After irradiating an electron beam of ˜5000 mJ / cm ² and heat-treating at 120 ° C. for 90 seconds, it was immersed in a 2.4% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) as an alkali agent at 25 ° C. for 4 minutes. The state after washing with water and drying was observed with a digital microscope (VH-6300VH, manufactured by Keyence Corporation) and evaluated according to the following criteria. The results are shown in Table 2A.

〔Evaluation criteria〕
○ ・ ・ ・ No exposure on the exposed surface △ ・ ・ ・ No dissolution

<Measurement method of surface roughness>
The surface roughness of the exposed surface is determined according to the method described in Masao Nagase, Waseda University Review Thesis 2475, “Study on Nanostructure Measurement by Atomic Force Microscope and its Application to Devices and Processes”, pp99-107 (1996). Using an electron beam drawing apparatus (CRESTEC, CABL9000), the surface of 30% of the exposure amount of the electron beam whose solubility was shown by the alkaline aqueous solution was measured. Electron beam irradiation is performed on a sample thin film having a thickness of about 300 nm formed on a silicon wafer on a square portion of 30 μm length × 30 μm width, heat treatment at 120 ° C. for 90 seconds, tetramethylammonium hydroxide. (TMAH) A surface that was immersed in a 2.4 mass% aqueous solution at 25 ° C. for 4 minutes, washed with water, and dried was used as an evaluation sample.

  The obtained evaluation sample was measured using an atomic force microscope (SPM-9500J3, manufactured by Shimadzu Corporation) according to the ten-point average roughness of JIS B0601-1994, which is an index of surface roughness. The results are shown in Table 2A.

(Example 1B)
-Synthesis of hyperbranched polymer-
In a 50 mL reaction vessel, 21 mmol of chloromethylstyrene as a reaction monomer, 13.1 mmol of 2,2-bipyridyl as a catalyst, 6.6 mmol of copper (I) chloride, and 8 mL of chlorobenzene as a solvent were accommodated. After substituting with argon, the mixture was stirred at a temperature of 115 ° C. for a polymerization reaction for 30 minutes. Tetrahydrofuran 50mL was added to this reaction liquid, the polymer was diluted and dissolved, and then the catalyst was removed by activated alumina filtration. After concentration of the filtrate, 200 mL of methanol was added to precipitate the polymer, and the unreacted monomer and the reaction solvent were removed by removing the supernatant. Next, the precipitated polymer was dissolved in 20 mL of tetrahydrofuran, 500 mL of methanol was added, and reprecipitation was repeated twice to synthesize the core part A (yield 60%).

  Next, in a 50 mL reaction vessel, 1 g of core part A as a raw material polymer, 33 mmol of acrylic acid-tert-butyl ester as a compound containing an acid-decomposable group, and 4.1 mmol of 2,2-bipyridyl as a catalyst Then, 2.1 mmol of copper (I) chloride and 13 mL of chlorobenzene as a solvent were accommodated, and the inside of the reaction vessel was purged with argon, and then stirred at a temperature of 125 ° C. for polymerization for 30 minutes. To this reaction solution, 50 mL of tetrahydrofuran was added to dilute and dissolve the produced polymer, and then the catalyst was removed by active alumina filtration. After concentration of the filtrate, 200 mL of methanol was added to precipitate the polymer, and the supernatant was removed to remove unreacted monomers and reaction solvent. Next, the precipitated polymer was dissolved in 20 mL of tetrahydrofuran, 500 mL of methanol was added, and reprecipitation was repeated twice to synthesize a hyperbranched polymer <1> into which the target acid-decomposable group represented by the following formula was introduced. .

  About the obtained core part A, the weight average molecular weight (Mw) and the branching degree (Br) were measured as follows. That is, the weight average molecular weight (Mw) of the core part A was determined by preparing a 0.05 wt% tetrahydrofuran solution and performing GPC measurement at a temperature of 40 ° C. Tetrahydrofuran was used as the mobile solvent. Styrene was used as a standard substance. The branching degree of the core part A was calculated by the mathematical formula (A) described above. The results are shown in Table 1B.

  Moreover, the weight average molecular weight (Mw) of the hyperbranched polymer <1> was measured by the same method as the weight average molecular weight (Mw) of the core part A. Furthermore, the introduction ratio of the acid-decomposable group was calculated by the above formula (a). The results are shown in Table 1B.

-Preparation of resist composition-
Propylene glycol monomethyl acetate solution containing 10% by weight of hyperbranched polymer <1> having an acid-decomposable group introduced and 0.5% by weight of triphenylsulfonium trifluoromethanesulfonate as a photoacid generator was prepared, and the content was 0.45 μm. The resist composition was prepared by filtration through a filter. Each of the obtained resist compositions was spin-coated on a silicon wafer, and the solvent was evaporated by a heat treatment at 90 ° C. for 1 minute to produce a thin film having a thickness of 300 nm, which was used as an evaluation sample.

<Alkali-soluble evaluation method>
The solubility in an alkaline aqueous solution is 50 in a rectangular portion of 3 μm in length and 50 μm in width with respect to a sample thin film having a thickness of about 300 nm formed on a silicon wafer using an electron beam drawing apparatus (CRESTEC, CABL9000). Irradiated with an electron beam of ˜5000 mJ / cm ² , after heat treatment at 100 ° C. for 4 minutes, it was immersed in a 2.4 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) as an alkali agent at 25 ° C. for 2 minutes. The state after washing with water and drying was observed with a digital microscope (VH-6300VH, manufactured by Keyence Corporation) and evaluated according to the following criteria. The results are shown in Table 2B.

〔Evaluation criteria〕
◎ ・ ・ ・ ・ There is no undissolved residue on the exposed surface and the edge is vertical ◎-○ ・ ・ There is no undissolved residue on the exposed surface and the edge is slightly inclined ○ ・ ・ ・ ・ Undissolved on the exposed surface A state where there is almost no ×× ・ ・ ・ A state where there is undissolved residue

<Measurement method of surface roughness>
The surface roughness of the exposed surface is determined according to the method described in Masao Nagase, Waseda University Review Thesis 2475, “Study on Nanostructure Measurement by Atomic Force Microscope and its Application to Devices and Processes”, pp99-107 (1996). Using an electron beam drawing apparatus (CRESTEC, CABL9000), the surface of 30% of the exposure amount of the electron beam whose solubility was shown by the alkaline aqueous solution was measured. Electron beam irradiation is performed on a sample thin film having a thickness of about 300 nm formed on a silicon wafer on a square portion of 30 μm in length and 30 μm in width, and after heat treatment at 100 ° C. for 4 minutes, tetramethylammonium hydro The surface which was immersed in an aqueous solution of 2.4% by weight of oxide (TMAH) at 25 ° C. for 2 minutes, washed with water and dried was used as an evaluation sample.

  The obtained evaluation sample was measured using an atomic force microscope (SPM-9500J3, manufactured by Shimadzu Corporation) according to the ten-point average roughness of JIS B0601-1994, which is an index of surface roughness. The results are shown in Table 2B.

(Example 2B)
-Synthesis of hyperbranched polymer-
The same as Example 1B, except that the amount of catalyst (2,2-bipyridyl and copper (I) chloride) in the hyperbranched polymer molecular core synthesis step was 0.8 times and the reaction temperature was 125 ° C. Thus, the core part B was synthesized (yield 77%). Further, the weight average molecular weight (Mw) and the degree of branching (Br) of the core part B were measured in the same manner as in Example 1B. The results are shown in Table 1B.

Next, 1 g of core part B as a raw material polymer in the acid-decomposable group introduction step, 0.8 times the amount of catalyst (2,2-bipyridyl and copper (I) chloride), and reaction time of 3 hours The hyperbranched polymer <2> was synthesized in the same manner as in Example 1B, except that the polymerization was conducted.
In the same manner as in Example 1B, the weight average molecular weight (Mw) of the obtained hyperbranched polymer <2> into which the acid-decomposable group was introduced was measured, and the number of monomers represented by Formula 1 constituting the core portion was measured. The introduction ratio of the acid-decomposable group was calculated by the formula (a). The results are shown in Table 1B.

-Preparation of resist composition-
A resist composition was prepared in the same manner as in Example 1B except that the hyperbranched polymer <2> into which an acid-decomposable group was introduced was used. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 3B)
-Synthesis of hyperbranched polymer-
A core portion C was synthesized in the same manner as in Example 1B except that the polymerization was performed at a reaction temperature of 125 ° C. in the hyperbranched polymer molecular core synthesis step (yield 78%). Further, the weight average molecular weight (Mw) and the degree of branching (Br) of the core part C were measured in the same manner as in Example 1B. The results are shown in Table 1B.

  Next, a hyperbranched polymer <3> was synthesized in the same manner as in Example 1B, except that 1 g of the core portion C as a raw material polymer in the acid-decomposable group introduction step was polymerized and the reaction time was 3 hours. .

  In the same manner as in Example 1B, the weight average molecular weight (Mw) of the obtained hyperbranched polymer <3> into which the acid-decomposable group was introduced was measured, and the number of monomers represented by Formula 1 constituting the core portion was measured. The introduction ratio of the acid-decomposable group was calculated by the formula (a). The results are shown in Table 1B.

-Preparation of resist composition-
An evaluation sample was prepared after preparing a resist composition in the same manner as in Example 1B, except that the hyperbranched polymer <3> into which an acid-decomposable group was introduced was used. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 4B)
-Synthesis of hyperbranched polymer-
Except for polymerizing 1 g of the core part B as a raw material polymer in the acid-decomposable group introduction step synthesized in Example 2B and 33 mmol of methacrylic acid-tert-butyl ester as a compound containing an acid-decomposable group, The target hyperbranched polymer <4> represented by the following formula was synthesized in the same manner as Example 2B.

  In the same manner as in Example 1B, the weight average molecular weight (Mw) of the obtained hyperbranched polymer <4> into which the acid-decomposable group was introduced was measured, and the number of monomers represented by Formula 1 constituting the core portion was measured. The introduction ratio of the acid-decomposable group was calculated by the formula (a). The results are shown in Table 1B.

-Preparation of resist composition-
A resist composition was prepared in the same manner as in Example 1B, except that the hyperbranched polymer <4> into which an acid-decomposable group was introduced was used. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 5B)
-Synthesis of hyperbranched polymer-
Example 2B except that 1 g of the core part B as a raw material polymer in the acid-decomposable group introduction step synthesized in Example 2B was polymerized as 33 g of tert-butoxystyrene as a compound containing an acid-decomposable group. In the same manner as described above, the desired hyperbranched polymer <5> represented by the following formula was synthesized.

  In the same manner as in Example 1B, the weight average molecular weight (Mw) of the obtained hyperbranched polymer <5> into which the acid-decomposable group was introduced was measured, and the number of monomers represented by Formula 1 constituting the core portion was measured. The introduction ratio of the acid-decomposable group was calculated by the formula (a). The results are shown in Table 1B.

-Preparation of resist composition-
A resist composition was prepared in the same manner as in Example 1B, except that the hyperbranched polymer <5> into which an acid-decomposable group was introduced was used. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 6B)
-Synthesis of hyperbranched polymer-
Except for polymerizing 1 g of the core part B as the raw material polymer in the acid-decomposable group introduction step synthesized in Example 2B and 33 mmol of the monomer represented by the formula (15) as a compound containing an acid-decomposable group, The target hyperbranched polymer <6> shown in the following formula was synthesized in the same manner as Example 2B.

  In the same manner as in Example 1B, the weight average molecular weight (Mw) of the obtained hyperbranched polymer <6> into which the acid-decomposable group was introduced was measured, and the number of monomers represented by Formula 1 constituting the core portion was measured. The introduction ratio of the acid-decomposable group was calculated by the formula (a). The results are shown in Table 1B.

-Preparation of resist composition-
A resist composition was prepared in the same manner as in Example 1B except that the hyperbranched polymer <6> into which an acid-decomposable group was introduced was used. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 7B)
-Synthesis of hyperbranched polymer-
Except that 1 g of the core part B as a raw material polymer in the acid-decomposable group introduction step synthesized in Example 2B and 33 mmol of the monomer represented by the formula (16) as a compound containing an acid-decomposable group were polymerized. The target hyperbranched polymer <7> shown in the following formula was synthesized in the same manner as Example 2B.

  In the same manner as in Example 1B, the weight average molecular weight (Mw) of the obtained hyperbranched polymer <7> into which the acid-decomposable group was introduced was measured, and the number of monomers represented by Formula 1 constituting the core portion was measured. The introduction ratio of the acid-decomposable group was calculated by the formula (a). The results are shown in Table 1B.

-Preparation of resist composition-
A resist composition was prepared in the same manner as in Example 1B except that the hyperbranched polymer <7> into which an acid-decomposable group was introduced was used. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 8B)
-Synthesis of hyperbranched polymer-
Except for polymerizing 1 g of the core part B as a raw material polymer in the acid-decomposable group introduction step synthesized in Example 2B and 33 mmol of the monomer represented by the formula (17) as a compound containing an acid-decomposable group, The target hyperbranched polymer <8> shown in the following formula was synthesized in the same manner as Example 2B.

  In the same manner as in Example 1B, the weight average molecular weight (Mw) of the obtained hyperbranched polymer <8> into which the acid-decomposable group was introduced was measured, and the number of monomers represented by Formula 1 constituting the core portion was measured. The introduction ratio of the acid-decomposable group was calculated by the formula (a). The results are shown in Table 1B.

-Preparation of resist composition-
A resist composition was prepared in the same manner as in Example 1B, except that the hyperbranched polymer <8> into which an acid-decomposable group was introduced was used. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 9B)
-Synthesis of hyperbranched polymer-
In formula (15), 1 g of core part B as a raw material polymer in the acid-decomposable group introduction step synthesized in Example 2B and 18 mmol of acrylic acid-tert-butyl ester as a compound containing an acid-decomposable group The target hyperbranched polymer <9> represented by the following formula was synthesized in the same manner as in Example 2B, except that the monomer shown was mixed with 18 mmol and polymerized.

  In the same manner as in Example 1B, the weight average molecular weight (Mw) of the obtained hyperbranched polymer <9> into which the acid-decomposable group was introduced was measured, and the number of monomers represented by Formula 1 constituting the core portion was measured. The introduction ratio of the acid-decomposable group was calculated by the formula (a). The results are shown in Table 1B.

-Preparation of resist composition-
A resist composition was prepared in the same manner as in Example 1B, except that the hyperbranched polymer <9> into which an acid-decomposable group was introduced was used. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 10B)
-Synthesis of hyperbranched polymer-
In a 50 mL reaction vessel, 1 g of core part B as a raw material polymer, 13.0 mmol of hydroquinone-tert-butyl ether as a compound containing an acid-decomposable group, and 13.0 mmol of NaH were stored, and 30 mL of tetrahydrofuran as a solvent. In addition, the mixture was reacted at a temperature of 70 ° C. under reflux for 5 hours. 200 mL of methanol was added to the reaction product, and the precipitated polymer was separated by decantation, washed with water and dried to synthesize a hyperbranched polymer <10> into which the target acid-decomposable group represented by the following formula was introduced.

  In the same manner as in Example 1B, the weight average molecular weight (Mw) of the obtained hyperbranched polymer <10> into which the acid-decomposable group was introduced was measured, and the number of monomers represented by Formula 1 constituting the core portion was measured. The introduction ratio of the acid-decomposable group was calculated by the formula (b). The results are shown in Table 1B.

-Preparation of resist composition-
A resist composition was prepared in the same manner as in Example 1B, except that the hyperbranched polymer <10> into which an acid-decomposable group was introduced was used. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 11B)
-Synthesis of hyperbranched polymer-
In Example 10B, except that 4-hydroxyphenyloxyacetic acid-tert-butyl ester as a compound containing an acid-decomposable group in the acid-decomposable group introduction step was 65 mmol and the reaction time was 3 hours. In the same manner as in 10B, reaction with 4-hydroxyphenyloxyacetic acid-tert-butyl ester and purification were carried out to synthesize a hyperbranched polymer <11> into which the target acid-decomposable group represented by the following formula was introduced.

  In the same manner as in Example 1B, the weight average molecular weight (Mw) of the obtained hyperbranched polymer <10> into which the acid-decomposable group was introduced was measured, and the number of monomers represented by Formula 1 constituting the core part was measured. The introduction ratio of the acid-decomposable group was calculated by the formula (b). The results are shown in Table 1B.

-Preparation of resist composition-
A resist composition was prepared in the same manner as in Example 1B except that the hyperbranched polymer <11> into which an acid-decomposable group was introduced was used. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 12B)
-Synthesis of hyperbranched polymer-
In a 50 ml reaction vessel, 1 g of hyperbranched polymer <2> synthesized in Example 2B as a raw material polymer, 4.1 mmol of 2,2-bipyridyl, copper (I) 2.1 mmol
l, 6.3 mmol of tri-n-butyltin hydride and 13 ml of chlorobenzene as a solvent were accommodated and stirred at a temperature of 60 ° C. for 24 hours. The target hyperbranched polymer <12> represented by the following formula was synthesized through the same filtration and precipitation purification as in Example 1B.

  In the same manner as in Example 1B, the weight average molecular weight (Mw) of the dehalogenated hyperbranched polymer <12> was measured. The results are shown in Table 1B.

(Example 13B)
-Synthesis of hyperbranched polymer-
In a 50 mL reaction vessel, 21 mmol of chloromethylstyrene as a reaction monomer, 10.5 mmol of 2,2-bipyridyl as a catalyst, 5.3 mmol of copper (I) chloride, and 8 mL of chlorobenzene as a solvent were accommodated. After substituting with argon, the mixture was stirred at a temperature of 125 ° C. for a polymerization reaction for 30 minutes.

  Next, without purification, 105 mmol of acrylic acid-tert-butyl ester as a compound containing an acid-decomposable group and 32 mL of chlorobenzene as a solvent are dropped into the same reaction vessel, and stirred at a temperature of 125 ° C. Polymerization was carried out. To this reaction solution, 50 mL of tetrahydrofuran was added to dilute and dissolve the produced polymer, and then the catalyst was removed by active alumina filtration. After concentration of the filtrate, 200 mL of methanol was added to precipitate the polymer, and the supernatant was removed to remove unreacted monomers and reaction solvent. Next, the precipitated polymer was dissolved in 20 mL of tetrahydrofuran, 500 mL of methanol was added, and reprecipitation was repeated twice to synthesize a hyperbranched polymer <13> into which the target acid-decomposable group was introduced. This is a case where the hyperbranched polymer molecular core synthesis step and the acid-decomposable group introduction step are performed continuously.

In the same manner as in Example 1B, the weight average molecular weight (Mw) of the obtained hyperbranched polymer <13> into which the acid-decomposable group was introduced was measured. Further, the amount of acid-decomposable group added is calculated by measuring the ¹ H-NMR of the product and calculating the ratio of the integral value of protons characteristic of the acid-decomposable group to the styrene-derived logarithm, which is the structural unit of the core part. did. The results are shown in Table 1B.

-Preparation of resist composition-
A resist composition was prepared in the same manner as in Example 1B, except that the hyperbranched polymer <13> into which an acid-decomposable group was introduced was used. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 14B)
-Synthesis of hyperbranched polymer-
Core portion D was synthesized (yield 76%) in the same manner as in Example 2B, except that polymerization was performed as chloromethylstyrene 18 mmol and styrene 2 mmol as reaction monomers in the hyperbranched polymer molecular core synthesis step. Moreover, the weight average molecular weight (Mw) of the core part D was measured like Example 1B. The results are shown in Table 1B.

  Next, a hyperbranched polymer <14> was synthesized in the same manner as in Example 2B, except that 1 g of the core portion D as the raw material polymer in the acid-decomposable group introduction step was polymerized. In the same manner as in Example 1B, the weight average molecular weight (Mw) of the obtained hyperbranched polymer <14> into which the acid-decomposable group was introduced was measured, and the number of monomers represented by Formula 1 constituting the core portion was measured. The introduction ratio of the acid-decomposable group was calculated by the above formula (c). The results are shown in Table 1B.

-Preparation of resist composition-
A resist composition was prepared in the same manner as in Example 1B, except that the hyperbranched polymer <14> into which an acid-decomposable group was introduced was used. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 15B)
-Synthesis of hyperbranched polymer-
The core portion E was synthesized in the same manner as in Example 2B except that 18 mmol of chloromethylstyrene as a reaction monomer in the hyperbranched polymer molecular core synthesis step and 2 mmol of acrylic acid-tert-butyl ester were polymerized (yield) 77%). Acrylic acid-tert-butyl ester is also an acid-decomposable group. Moreover, the weight average molecular weight (Mw) of the core part E was measured like Example 1B. The results are shown in Table 1B.

Next, a hyperbranched polymer <15> was synthesized in the same manner as in Example 2B, except that 1 g of the core portion E as a raw material polymer in the acid-decomposable group introduction step was polymerized. In the same manner as in Example 1B, the weight average molecular weight (Mw) of the obtained hyperbranched polymer <15> into which the acid-decomposable group was introduced was measured, and the number of monomers represented by Formula 1 constituting the core portion was measured. The introduction ratio of the acid-decomposable group was calculated by the formula (c). The results are shown in Table 1B.
-Preparation of resist composition-

  A resist composition was prepared in the same manner as in Example 1B except that the hyperbranched polymer <15> into which an acid-decomposable group was introduced was used. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 16B)
-Synthesis of hyperbranched polymer-
The core portion F was synthesized in the same manner as in Example 2B, except that polymerization was performed as chloromethylstyrene 16 mmol, styrene 2 mmol, and tert-butoxystyrene 2 mmol as reaction monomers in the hyperbranched polymer molecular core synthesis step (yield) 80%). Note that tert-butoxystyrene is also an acid-decomposable group. Moreover, the weight average molecular weight (Mw) of the core part F was measured like Example 1B. The results are shown in Table 1B.

  Next, a hyperbranched polymer <16> was synthesized in the same manner as in Example 2B, except that 1 g of the core portion F as a raw material polymer in the acid-decomposable group introduction step was polymerized. In the same manner as in Example 1B, the weight average molecular weight (Mw) of the obtained hyperbranched polymer <16> into which the acid-decomposable group was introduced was measured, and the number of monomers represented by Formula 1 constituting the core portion was measured. The introduction ratio of the acid-decomposable group was calculated by the formula (c). The results are shown in Table 1B.

-Preparation of resist composition-
A resist composition was prepared in the same manner as in Example 1B, except that the hyperbranched polymer <16> into which an acid-decomposable group was introduced was used. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 17B)
-Synthesis of hyperbranched polymer-
Example 2B, except that 1 g of the core part D as a raw material polymer in the acid-decomposable group introduction step synthesized in Example 14B and 33 mmol of tert-butoxystyrene as a compound containing an acid-decomposable group were polymerized. The target hyperbranched polymer <17> was synthesized in the same manner as described above.

  In the same manner as in Example 1B, the weight average molecular weight (Mw) of the obtained hyperbranched polymer <17> into which the acid-decomposable group was introduced was measured, and the number of monomers represented by Formula 1 constituting the core portion was measured. The introduction ratio of the acid-decomposable group was calculated by the formula (c). The results are shown in Table 1B.

-Preparation of resist composition-
A resist composition was prepared in the same manner as in Example 1B except that the hyperbranched polymer <17> into which an acid-decomposable group was introduced was used. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 18B)
-Synthesis of hyperbranched polymer-
Example 2B, except that 1 g of the core part E as a raw material polymer in the acid-decomposable group introduction step synthesized in Example 15B and 33 mmol of tert-butoxystyrene as a compound containing an acid-decomposable group were polymerized. The target hyperbranched polymer <18> was synthesized in the same manner as described above.

  In the same manner as in Example 1B, the weight average molecular weight (Mw) of the obtained hyperbranched polymer <18> into which the acid-decomposable group was introduced was measured, and the number of monomers represented by Formula 1 constituting the core portion was measured. The introduction ratio of the acid-decomposable group was calculated by the formula (c). The results are shown in Table 1B.

-Preparation of resist composition-
A resist composition was prepared in the same manner as in Example 1B, except that the hyperbranched polymer <18> into which an acid-decomposable group was introduced was used. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 19B)
-Synthesis of hyperbranched polymer-
Example 2B, except that 1 g of the core part F as a raw material polymer and 33 mmol of tert-butoxystyrene as a compound containing an acid-decomposable group were polymerized in the acid-decomposable group introduction step synthesized in Example 16B. In the same manner as described above, the desired hyperbranched polymer <19> represented by the following formula was synthesized.

  In the same manner as in Example 1B, the weight average molecular weight (Mw) of the obtained hyperbranched polymer <19> into which the acid-decomposable group was introduced was measured, and the number of monomers represented by Formula 1 constituting the core portion was measured. The introduction ratio of the acid-decomposable group was calculated by the formula (c). The results are shown in Table 1B.

-Preparation of resist composition-
A resist composition was prepared in the same manner as in Example 1B except that the hyperbranched polymer <19> into which an acid-decomposable group was introduced was used. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 20B)
-Preparation of resist composition-
Resist was prepared in the same manner as in Example 1B except that 10% by weight of hyperbranched polymer <2> having an acid-decomposable group introduced and 0.5% by weight of bis (cyclohexylsulfonyl) diazomethane as a photoacid generator were used. A composition was prepared. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 21B)
-Preparation of resist composition-
Except that 10% by weight of hyperbranched polymer <2> having an acid-decomposable group introduced and 0.5% by weight of bis (tert-butylsulfonyl) diazomethane as a photoacid generator were used, in the same manner as in Example 1B. A resist composition was prepared. Further, as in Example 1B, alkali solubility was evaluated and surface roughness was measured. The results are shown in Table 2B.

(Example 1C)
-Synthesis of hyperbranched polymer-
In a 1000 mL reaction vessel, 630 mmol of chloromethylstyrene as a reaction monomer, 315 mmol of 2,2-bipyridyl as a catalyst, 157.5 mmol of copper (I) chloride, and 480 mL of chlorobenzene as a solvent are accommodated, and the inside of the reaction vessel is replaced with argon. Then, the polymerization reaction was carried out for 27 minutes with stirring at a temperature of 125 ° C. Tetrahydrofuran 100mL was added to this reaction liquid, the polymer was diluted and dissolved, and then the catalyst was removed by activated alumina filtration. After concentration of the filtrate, 700 mL of methanol was added to precipitate the polymer, and the unreacted monomer and the reaction solvent were removed by removing the supernatant. Then, 600 mL of a mixed solvent of tetrahydrofuran and methanol (mixing ratio 8: 2 mL / mL) was added to the polymer dried under reduced pressure, followed by stirring and washing. This washing operation was repeated twice to synthesize a core part G having a weight average molecular weight (Mw) of 2,000 and a branching degree of 0.47 (yield 77%).

  Next, in a 1000 mL reaction vessel, 16.2 g of core part G as a raw material polymer, 76 mmol of acrylic acid-tert-butyl ester as a compound containing an acid-decomposable group, 53 mmol of 2,2-bipyridyl as a catalyst Then, 26 mmol of copper (I) chloride and 400 mL of chlorobenzene as a solvent were housed, and the inside of the reaction vessel was purged with argon, followed by stirring at a temperature of 125 ° C. for polymerization for 5 hours. Tetrahydrofuran (100 mL) was added to the reaction solution to dilute and dissolve the produced polymer, and then the catalyst was removed by active alumina filtration. After concentration of the filtrate, 750 mL of methanol was added to precipitate the polymer, and the supernatant was removed to remove unreacted monomers and reaction solvent. Next, the precipitated polymer was dissolved in 50 mL of tetrahydrofuran, 500 mL of methanol was added, and reprecipitation was repeated twice to synthesize a hyperbranched polymer <20> into which the target acid-decomposable group was introduced.

  Next, 0.5 g of <20>, 0.75 mL of 10N hydrochloric acid, and 25 mL of dioxane were placed in a 50 mL reaction vessel, and the acid-decomposable group was partially decomposed by heating and stirring at a temperature of 85 ° C. for 60 minutes. This reaction solution was poured into 250 mL of water to precipitate a polymer. Subsequently, the operation of dissolving the precipitated polymer except for the supernatant liquid in dioxane and reprecipitating from water was repeated to synthesize a hyperbranched polymer <21> into which a carboxyl group represented by the following formula was introduced.

The weight average molecular weight of the obtained hyperbranched polymer <21> was determined by the above GPC measurement. The composition of the obtained hyperbranched polymer was measured by ¹ H-NMR and calculated from the integral value of protons characteristic of the acid-decomposable group. The results are shown in Table 1C.

-Removal of copper element in polymer-
A propylene glycol monomethyl acetate (PEGMEA) solution containing 7.5% by weight of hyperbranched polymer <21> was prepared, and copper element removal treatment was performed by ion exchange membrane and membrane membrane treatment. First, three membranes of Protego CP manufactured by Nihon Microlith Co., Ltd. cut into a circular shape with a diameter of 47 mm as an ion exchange membrane on the upper layer, and a membrane filter with a pore diameter of 0.05 μm and a 47 mm diameter membrane filter manufactured by Millipore are stacked on the lower layer. A filter was used, and metal removal was performed by flowing 10 ml of the polymer solution at a flow rate of 4 ml / min by pressure filtration. The amount of copper element remaining in the sample subjected to the removal treatment was quantified using a P-6000 type MIP-MS (copper element detection limit 50 ppb) manufactured by Hitachi, Ltd., using an organometallic standard solution manufactured by CONOSTAN as a standard substance. The results are shown in Table 1C.

-Preparation of resist composition-
Propylene glycol monomethyl acetate (PEGMEA) solution containing 4% by weight of hyperbranched polymer <21> treated with copper element removal and 0.04% by weight of triphenylsulfonium trifluoromethanesulfonate as a photoacid generator was prepared. The resist composition was prepared by filtering through a 0.45 μm filter. The obtained resist composition was spin-coated on a silicon wafer, and the solvent was evaporated by a heat treatment at 90 ° C. for 1 minute to prepare a thin film having a thickness of 100 nm.

-Evaluation of alkali solubility-
The alkali solubility is a rectangular shape measuring 10 mm long by 3 mm wide with respect to a sample thin film of about 100 nm formed on a silicon wafer using a discharge tube type ultraviolet irradiation device (DF-245 type Donafix manufactured by ATTO Corporation). The part was irradiated with ultraviolet rays having a wavelength of 245 nm energy of 0 to 200 mJ / cm 2, heat treatment at 100 ° C. for 4 minutes, and then at 25 ° C. in a 2.4 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) as an alkali agent. The film thickness after immersion for 2 minutes, washing with water and drying was measured with a thin film measuring apparatus F20 manufactured by Filmetics Co., Ltd., and evaluated according to the following criteria.

Unexposed area Exposed area ○ …… Reduced film thickness 0 to less than 30% ○ ・ ・ ・ ・ ・ Reduced film thickness 100%
△ ... Decrease in film thickness 30 to less than 50% △ ... Decrease in film thickness Less than 100 to 90%
× ··· Reduced film thickness 50 to 100% × · · Reduced film thickness less than 90%

  In addition, after being immersed in a 2.4% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) at 25 ° C. for 2 minutes, the minimum ultraviolet ray (254 nm) irradiation dose at which the reduction of the film thickness at the exposed area becomes 100% is measured as sensitivity. did. The results are shown in Table 2C.

-Measurement of surface roughness-
For the surface roughness of the exposed surface, refer to the method described in Masao Nagase, Waseda University Examination Thesis 2475, “Study on Nanostructure Measurement by Atomic Force Microscope and its Application to Devices and Processes”, pp99-107 (1996). The surface of 30% of the exposure amount of ultraviolet rays (245 nm) whose solubility was shown by the above alkaline aqueous solution was measured using a discharge tube type ultraviolet irradiation device (manufactured by Ato Co., Ltd., DF-245 type Donfix). Irradiation with ultraviolet rays is performed on a sample thin film having a thickness of about 500 nm formed on a silicon wafer on a rectangular portion of 10 mm in length and 3 mm in width. After heat treatment at 100 ° C. for 4 minutes, tetramethylammonium hydroxide is applied. (TMAH) A surface that was immersed in a 2.4 mass% aqueous solution at 25 ° C. for 2 minutes, washed with water, and dried was used as an evaluation sample.

  The obtained evaluation sample was measured using an atomic force microscope (SPM-9500J3, manufactured by Shimadzu Corporation) according to the ten-point average roughness of JIS B0601-1994, which is an index of surface roughness. The results are shown in Table 2C.

(Example 2C)
-Synthesis of hyperbranched polymer-
In a 50 mL reaction vessel, 8.0 g of the hyperbranched polymer <20> described in Example 1C was accommodated in 12.0 mL of 10N hydrochloric acid and 400 mL of dioxane, and heated and stirred at a temperature of 85 ° C. for 65 minutes to remove the acid-decomposable group. Partially disassembled. A hyperbranched polymer <22> into which a carboxyl group was introduced was synthesized by the same purification and copper element removal treatment as in Example 1C. The results are shown in Table 1C.

-Preparation of resist composition-
An evaluation sample was prepared after preparing a resist composition in the same manner as in Example 1C except that the hyperbranched polymer <22> was used. In addition, as in Example 1C, alkali solubility was evaluated, and sensitivity and surface roughness were measured. The results are shown in Table 2C.

(Example 3C)
-Synthesis of hyperbranched polymer-
A 500 mL reaction vessel contains 210 mmol of chloromethylstyrene as a reaction monomer, 105 mmol of 2,2-bipyridyl as a catalyst, 52.5 mmol of copper (I) chloride, and 160 mL of chlorobenzene as a solvent, and the inside of the reaction vessel is purged with argon. Then, the mixture was stirred at a temperature of 125 ° C. and polymerized for 40 minutes. Tetrahydrofuran 100mL was added to this reaction liquid, the polymer was diluted and dissolved, and then the catalyst was removed by activated alumina filtration. After concentration of the filtrate, 200 mL of methanol was added to precipitate the polymer, and the unreacted monomer and the reaction solvent were removed by removing the supernatant. Next, 200 mL of a tetrahydrofuran / methanol mixed solvent (mixing ratio 7: 3 mL / mL) was added to the polymer dried under reduced pressure, followed by stirring and washing. This washing operation was repeated twice to synthesize a core part H having a weight average molecular weight (Mw) of 4,000 and a branching degree of 0.50 (yield 70%).

  Next, in a 1000 mL reaction vessel, 13.1 g of core part H as a raw material polymer, 62 mmol of acrylic acid-tert-butyl ester as a compound containing an acid-decomposable group, and 2,2-bipyridyl 42 as a catalyst .9 mmol, 21.5 mmol of copper (I) chloride, and 327 mL of chlorobenzene as a solvent were accommodated, and the inside of the reaction vessel was purged with argon, followed by stirring at a temperature of 125 ° C. for polymerization for 5 hours. The hyperbranched polymer <23> into which the target acid-decomposable group was introduced was synthesized by the same purification as in Example 1C.

  Next, 0.5 g of <23> and 0.5 mL of 10N hydrochloric acid and 25 mL of dioxane were accommodated in a 50 mL reaction vessel, and the acid-decomposable group was partially decomposed by heating and stirring at a temperature of 90 ° C. for 60 minutes. A hyperbranched polymer <24> into which a carboxyl group was introduced was synthesized by the same purification and copper element removal treatment as in Example 1C. The results are shown in Table 1C.

-Preparation of resist composition-
An evaluation sample was prepared after preparing a resist composition in the same manner as in Example 1C except that the hyperbranched polymer <24> was used. In addition, as in Example 1C, alkali solubility was evaluated, and sensitivity and surface roughness were measured. The results are shown in Table 2C.

(Example 4C)
-Synthesis of hyperbranched polymer-
In a 50 mL reaction vessel, 12.0 g of hyperbranched polymer <23> described in Example 3C and 24.0 mL of 10N hydrochloric acid and 600 mL of dioxane were placed, and the acid-decomposable group was removed by heating and stirring at 90 ° C. for 60 minutes. Partially disassembled. A hyperbranched polymer <25> into which a carboxyl group was introduced was synthesized by the same purification and copper element removal treatment as in Example 1C. The results are shown in Table 1C.

-Preparation of resist composition-
An evaluation sample was prepared after preparing a resist composition in the same manner as in Example 1C except that the hyperbranched polymer <25> was used. In addition, as in Example 1C, alkali solubility was evaluated, and sensitivity and surface roughness were measured. The results are shown in Table 2C.

(Example 5C)
-Synthesis of hyperbranched polymer-
In a 1000 mL reaction vessel, 14.7 g of core part H as a raw material polymer, 63 mmol of acrylic acid-tert-butyl ester as a compound containing an acid-decomposable group, 24.1 mmol of 2,2-bipyridyl as a catalyst, and After containing 12.1 mmol of copper (I) chloride and 366 mL of chlorobenzene as a solvent, the reaction vessel was purged with argon, and then stirred at a temperature of 125 ° C. for polymerization for 3 hours. The hyperbranched polymer <26> into which the target acid-decomposable group was introduced was synthesized by the same purification as in Example 1C.

  Next, 12.0 g of <26> and 54 mL of 10N hydrochloric acid and 600 mL of dioxane were accommodated in a 1000 mL reaction vessel, and the acid-decomposable group was partially decomposed by heating and stirring at a temperature of 90 ° C. for 60 minutes. A hyperbranched polymer <27> into which a carboxyl group was introduced was synthesized by the same purification and copper element removal treatment as in Example 1C. The results are shown in Table 1C.

-Preparation of resist composition-
An evaluation sample was prepared after preparing a resist composition in the same manner as in Example 1C except that the hyperbranched polymer <27> was used. In addition, as in Example 1C, alkali solubility was evaluated, and sensitivity and surface roughness were measured. The results are shown in Table 2C.

(Example 6C)
-Synthesis of hyperbranched polymer-
In a 50 mL reaction vessel, 0.6 g of the hyperbranched polymer <26> described in Example 5C was accommodated in 2.4 mL of 10N hydrochloric acid and 30 mL of dioxane, and the mixture was heated and stirred at 90 ° C. for 60 minutes to remove the acid-decomposable group. Partially disassembled. A hyperbranched polymer <28> into which a carboxyl group was introduced was synthesized by the same purification and copper element removal treatment as in Example 1C. The results are shown in Table 1C.

-Preparation of resist composition-
An evaluation sample was prepared after preparing a resist composition in the same manner as in Example 1C except that the hyperbranched polymer <28> was used. In addition, as in Example 1C, alkali solubility was evaluated, and sensitivity and surface roughness were measured. The results are shown in Table 2C.

(Example 7C)
-Synthesis of hyperbranched polymer-
In a 50 mL reaction vessel, 0.6 g of the hyperbranched polymer <26> described in Example 5C was stored, 2.7 mL of 10N hydrochloric acid, and 30 mL of dioxane, and the mixture was heated and stirred at 90 ° C. for 60 minutes to remove the acid-decomposable group. Partially disassembled. A hyperbranched polymer <29> into which a carboxyl group was introduced was synthesized by the same purification and copper element removal treatment as in Example 1C. The results are shown in Table 1C.

-Preparation of resist composition-
An evaluation sample was prepared after preparing a resist composition in the same manner as in Example 1C except that the hyperbranched polymer <29> was used. In addition, as in Example 1C, alkali solubility was evaluated, and sensitivity and surface roughness were measured. The results are shown in Table 2C.

  From the above results, it was found that the resist composition using the hyperbranched polymer of the present invention has excellent solubility and surface smoothness in electron beam lithography or optical lithography. In particular, as is clear from Examples 1B, 2B, and 12B to 15B in Table 2B, a resist containing a polymer into which acrylic acid-tert-butyl ester has been introduced at an introduction ratio of 1 or more has vertical edges, and surface roughness From the fact that is extremely small, it was found that it is suitable for the formation of ultrafine patterns. Moreover, from the results of Tables 1C and 2C, particularly from the results of Examples 2C and 7C, the copper element derived from the polymerization catalyst having an acid-decomposable group consisting of acrylic acid-tert-butyl ester and acrylic acid was removed to the ppb order. It has been found that a resist composition using a hyperbranched polymer has extremely high sensitivity and sufficiently satisfies the sensitivity required in high-throughput lithography.

  In addition, this invention has the following 1-20 inventions.

(Invention 1) A hyperbranched polymer having an acid-decomposable group at a polymer molecule terminal.

(Invention 2) A hyperbranched polymer having an acid-decomposable group at a molecular end of a hyperbranched polymer obtained by subjecting a styrene derivative to a living radical polymerization reaction.

（式（１）において、Ｙは、ヒドロキシル基又はカルボキシル基を含んでいてもよい炭素数１〜１０のアルキレン基を表す。Ｚは、ハロゲン原子を示す。）

（式（２）〜（５）において、Ｒ¹は水素原子又は炭素数１〜３のアルキル基を表わす。Ｒ²、Ｒ³は水素原子、炭素数１〜３０の直鎖状、分岐状もしくは環状のアルキル基、又は炭素数６〜３０のアリール基を表わし、Ｒ²、Ｒ³は互いに同一でも異なっていてもよい。Ｒ⁴は水素原子；炭素数１〜４０の直鎖状、分岐状もしくは環状のアルキル基；トリアルキルシリル基（ここで、各アルキル基の炭素数は１〜６である）；オキソアルキル基（ここで、アルキル基の炭素数は４〜２０である）；又は下記式（６）で表される基（ただし、Ｒ⁵は直鎖状、分岐鎖状、もしくは環状の炭素数１〜１０のアルキル基、Ｒ⁶、Ｒ⁷は互いに独立して水素原子、直鎖状、分岐鎖状又は環状の炭素数１〜１０のアルキル基を示すか、或いはＲ⁶、Ｒ⁷が直鎖状又は分岐鎖状の炭素数１〜１０のアルキル基を表すとき、互いに一緒になって環を形成してもよい）を表す。ｎは０から１０の整数を示す。）

(Invention 3) The core part in the hyperbranched polymer is a homopolymer of a monomer represented by the following formula (1), or a monomer represented by the following formula (1) and the following formula (2) to (5) The hyperbranched polymer according to the invention 1, which is a copolymer with at least one monomer selected from

(In Formula (1), Y represents a C1-C10 alkylene group which may contain a hydroxyl group or a carboxyl group. Z represents a halogen atom.)

(In the formulas (2) to (5), R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ² and R ³ are a hydrogen atom, a straight chain having 1 to 30 carbon atoms, branched or Represents a cyclic alkyl group or an aryl group having 6 to 30 carbon atoms, and R ² and R ³ may be the same or different from each other, R ⁴ is a hydrogen atom; Or a cyclic alkyl group; a trialkylsilyl group (wherein each alkyl group has 1 to 6 carbon atoms); an oxoalkyl group (wherein the alkyl group has 4 to 20 carbon atoms); or A group represented by formula (6) (wherein R ⁵ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, R ⁶ and R ⁷ are each independently a hydrogen atom, a linear chain, Jo, or shows a branched or cyclic alkyl group having 1 to 10 carbon atoms, or R ^6, R ⁷ is a straight When referring to Jo or branched alkyl group having 1 to 10 carbon atoms, .n representing the or) to form a ring together with each other represent an integer of 0 to 10.)

（式（I）〜（IV）において、Ｒ^1'及びＲ^2'はそれぞれＲ¹及びＲ²について定義したのと同じであり、Ｒ⁸は水素原子；炭素数３〜４０の直鎖状、分岐状もしくは環状のアルキル基；トリアルキルシリル基（ここで、各アルキル基の炭素数は１〜６である）；オキソアルキル基（ここで、アルキル基の炭素数は４〜２０である）；又は上記式（６）で表される基を示す。Ｒ⁹及びＲ¹⁰は、水素原子；直鎖状、分岐鎖状もしくは環状の炭素数１〜１０のアルキル基；又は炭素数６〜３０のアリール基を示し、Ｒ⁹及びＲ¹⁰は互いに同一でも異なっていてもよく、Ｒ⁹、Ｒ¹⁰は互いに一緒になって環を形成してもよい。Ｇはハロゲン原子；水素原子；直鎖状、分岐鎖状もしくは環状の炭素数１〜１０のアルキル基；炭素数６〜３０のアリール基；アルキルカルボニルオキシ基（ここで、アルキル基の炭素数は１〜１０である）、アルキルオキシ基（ここで、アルキル基の炭素数は１〜１０である）、フェニルオキシ基、チオエーテル基、アミノ基又はシアノ基を示す。ｍは０から１０の整数を示し、ａ、ｂ、ｃ及びｄはそれぞれ１以上の整数を示す。）
−Ｘ−Ｗ （７）
（式（７）において、Ｘは、酸素原子、硫黄原子、窒素原子、炭素数１〜６の直鎖状もしくは分岐鎖状アルキレン基、又は原子間結合を表わし、Ｗは、水素原子、炭素数１〜１０の直鎖状、分岐状もしくは環状のアルキル基；フェニル基；炭素数７〜２０のアルコキシフェニル基、炭素数２〜１０のアルコキシカルボニル基、又は下記式（８）で表される基を示す。
−Ｒ¹¹−ＣＯＯ−Ｒ^8' （８）
（式（８）において、Ｒ¹¹は、炭素数１〜３０の直鎖状、分岐状、環状のアルキレン基、又は炭素数６〜３０のアリーレン基を表し、エーテル結合又はエステル結合を含んでいてもよい。Ｒ^8'はＲ⁸について記載したのと同じである。）） (Invention 4) Any of the inventions 1 to 3, wherein the acid-decomposable group in the hyperbranched polymer is at least one group selected from the group consisting of the following formulas (I) to (IV) and formula (7): The hyperbranched polymer according to claim 1.

(In the formulas (I) to (IV), R ^{1 ′} and R ^{2 ′} are the same as defined for R ¹ and R ^2, respectively; R ⁸ is a hydrogen atom; A branched or cyclic alkyl group; a trialkylsilyl group (wherein each alkyl group has 1 to 6 carbon atoms); an oxoalkyl group (wherein the alkyl group has 4 to 20 carbon atoms); Or a group represented by the above formula (6), wherein R ⁹ and R ¹⁰ are a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms; R ⁹ and R ¹⁰ may be the same or different from each other, and R ⁹ and R ¹⁰ may be combined with each other to form a ring, G is a halogen atom; A branched or cyclic alkyl group having 1 to 10 carbon atoms; an aryl group having 6 to 30 carbon atoms; Killcarbonyloxy group (wherein the alkyl group has 1 to 10 carbon atoms), alkyloxy group (wherein the alkyl group has 1 to 10 carbon atoms), phenyloxy group, thioether group, amino group Or a cyano group, m represents an integer of 0 to 10, and a, b, c and d each represents an integer of 1 or more.)
-X-W (7)
(In Formula (7), X represents an oxygen atom, a sulfur atom, a nitrogen atom, a linear or branched alkylene group having 1 to 6 carbon atoms, or an interatomic bond, and W represents a hydrogen atom or a carbon number. A linear, branched or cyclic alkyl group having 1 to 10; a phenyl group; an alkoxyphenyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or a group represented by the following formula (8): Indicates.
—R ¹¹ —COO—R ^{8 ′} (8)
(In Formula (8), R ¹¹ represents a linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms, or an arylene group having 6 to 30 carbon atoms, and includes an ether bond or an ester bond. R ^{8 ′} is the same as described for R ⁸ ))

(Invention 5) The hyperbranched polymer is a homopolymer of the monomer represented by the formula (1) or the monomer represented by the formula (1) and the monomer represented by the formulas (2) to (5). A core part which is a copolymer with at least one selected from the group consisting of: and an acid-decomposable group represented by the formula (I), (II), (III) or (7) The hyperbranched polymer according to the invention 3 or 4 above.

(Invention 6) The hyperbranched polymer is a homopolymer of the monomer represented by the formula (1) or the monomer represented by the formula (1) and the monomer represented by the formulas (2) to (4). The invention 3 above, comprising a core part which is a copolymer with at least one selected from the group consisting of: and an acid-decomposable group represented by the formula (I), (III) or (IV). Or the hyperbranched polymer of 4.

(Invention 7) The core portion, wherein the hyperbranched polymer is a copolymer with at least one selected from the group consisting of monomers represented by the formula (2), (4) or (5), and the formula The hyperbranched polymer according to the invention 3 or 4, which comprises an acid-decomposable group represented by (IV).

(Invention 8) The hyperbranched polymer according to any one of Inventions 3 to 7, wherein the monomer represented by the formula (1) is an alkylene group having 1 to 8 carbon atoms in the formula (1).

(Invention 9) The hyperbranched polymer according to any one of Inventions 3 to 8, wherein the monomer represented by the formula (1) is chloromethylstyrene.

(Invention 10) The hyperbranched polymer according to any one of Inventions 1 to 9, wherein the hyperbranched polymer has a weight average molecular weight (Mw) of 2,000 to 150,000.

(Invention 11) The resist composition according to Invention 10, wherein the hyperbranched polymer has a weight average molecular weight (Mw) of 500 to 150,000.

(Invention 12) In the inventions 4 to 11, the monomer unit constituting the core portion of the hyperbranched polymer is contained in an amount of 10 to 90 mol% with respect to the monomer unit constituting the hyperbranched polymer. The hyperbranched polymer according to any one of the above.

(Invention 13) At least one repeating unit selected from the above formulas (I) to (IV) constituting the acid-decomposable group is contained in an amount of 10 to 90 mol% based on the monomer unit constituting the hyperbranched polymer. The hyperbranched polymer according to any one of the above inventions 4 to 11, wherein

(Invention 14) The group represented by the formula (7) constituting the acid-decomposable group is contained in an amount of 10 to 50 mol% with respect to the monomer unit constituting the hyperbranched polymer. The hyperbranched polymer according to any one of Inventions 4 to 11.

(Invention 15) A monomer in which, in at least one repeating unit selected from the formulas (I) to (IV) constituting the acid-decomposable group, a repeating unit in which R ⁸ is a hydrogen atom constitutes the hyperbranched polymer. The hyperbranched polymer according to any one of the inventions 4 to 11, which is contained in an amount of 0 to 70 mol% based on the unit.

(Invention 16) The hyperbranched polymer according to any one of Inventions 1 to 15, wherein the amount of metal element contained in the hyperbranched polymer is less than 100 ppb.

(Invention 17) The monomer represented by the formula (1) is subjected to living radical polymerization alone or at least one selected from the monomer represented by the formula (1) and the formulas (2) to (5). A step of living radical polymerization of the monomer, and a step of introducing an acid-decomposable group into the polymer by reacting the polymer obtained in the step with a compound containing an acid-decomposable group. A method for producing a hyperbranched polymer.

（式（１）において、Ｙは、ヒドロキシル基又はカルボキシル基を含んでいてもよい炭素数１〜１０のアルキレン基を表す。Ｚは、ハロゲン原子を示す。） (Invention 18) A hyperbranched polymer synthesizing step for synthesizing a hyperbranched polymer by subjecting a monomer represented by the following formula (1) to a living radical polymerization reaction; and A method for producing a hyperbranched polymer, comprising: an acid-decomposable group introducing step of reacting and introducing an acid-decomposable group into a terminal of the hyperbranched polymer.

(In Formula (1), Y represents a C1-C10 alkylene group which may contain a hydroxyl group or a carboxyl group. Z represents a halogen atom.)

(Invention 19) A resist composition containing the hyperbranched polymer according to any one of Inventions 1 to 16.

(Invention 20) The resist composition according to the invention 19, further comprising a photoacid generator.

  The hyperbranched polymer of the present invention can be suitably used as a base resin for resist materials corresponding to electron beams, deep ultraviolet (DUV), and extreme ultraviolet (EUV) light sources whose surface smoothness is required on the nano order.

  The resist composition of the present invention can form a fine pattern for the production of VLSI, and can cope with the formation of an ultrafine pattern of 50 nm or less that will be required in the future.

Claims (9)

  A resist composition comprising a hyperbranched polymer having an acid-decomposable group at a polymer molecule terminal.   The resist composition according to claim 1, wherein the hyperbranched polymer is obtained by subjecting a styrene derivative to a living radical polymerization reaction. The resist composition according to claim 1, wherein the core portion of the hyperbranched polymer is a polymer of a monomer represented by the following formula (1).

The resist composition according to claim 3, wherein the core portion of the hyperbranched polymer is a homopolymer of a monomer represented by the following formula (1).

The core portion in the hyperbranched polymer is a copolymer of a monomer represented by the following formula (1) and at least one monomer selected from the following (2) to (5). 3. The resist composition according to 3.

(In Formula (1), Y represents a C1-C10 alkylene group which may contain a hydroxyl group or a carboxyl group. Z represents a halogen atom.)

(In the formulas (2) to (5), R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ² and R ³ are a hydrogen atom, a straight chain having 1 to 30 carbon atoms, branched or Represents a cyclic alkyl group or an aryl group having 6 to 30 carbon atoms, and R ² and R ³ may be the same as or different from each other, R ⁴ represents a hydrogen atom; Or a cyclic alkyl group; a trialkylsilyl group (wherein each alkyl group has 1 to 6 carbon atoms); an oxoalkyl group (wherein the alkyl group has 4 to 20 carbon atoms); or A group represented by formula (6) (wherein R ⁵ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, R ⁶ and R ⁷ are each independently a hydrogen atom, a linear chain, Jo, or shows a branched or cyclic alkyl group having 1 to 10 carbon atoms, or R ^6, R ⁷ is a straight When referring to Jo or branched alkyl group having 1 to 10 carbon atoms, .n representing the good) to form a ring together with each other represent an integer of 0 to 10.)

The resist composition according to claim 1, wherein the acid-decomposable group in the hyperbranched polymer is at least one group selected from the group consisting of the following formulas (I) to (IV).

(In the formulas (I) to (IV), R ^{1 ′} and R ^{2 ′} are the same as defined for R ¹ and R ^2, respectively; R ⁸ is a hydrogen atom; A branched or cyclic alkyl group; a trialkylsilyl group (wherein each alkyl group has 1 to 6 carbon atoms); an oxoalkyl group (wherein the alkyl group has 4 to 20 carbon atoms); Or a group represented by the above formula (6), wherein R ⁹ and R ¹⁰ are a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms; R ⁹ and R ¹⁰ may be the same or different from each other, and R ⁹ and R ¹⁰ may be combined with each other to form a ring, G is a halogen atom; A branched or cyclic alkyl group having 1 to 10 carbon atoms; an aryl group having 6 to 30 carbon atoms; Killcarbonyloxy group (wherein the alkyl group has 1 to 10 carbon atoms), alkyloxy group (wherein the alkyl group has 1 to 10 carbon atoms), phenyloxy group, thioether group, amino group Or a cyano group, m represents an integer of 0 to 10, and a, b, c and d each represents an integer of 1 or more.) The resist composition according to claim 1, wherein the acid-decomposable group in the hyperbranched polymer includes a group represented by the following formula (7).
-X-W (7)
(In Formula (7), X represents an oxygen atom, a sulfur atom, a nitrogen atom, a linear or branched alkylene group having 1 to 6 carbon atoms, or an interatomic bond, and W represents a hydrogen atom or a carbon number. 1-10 linear, branched or cyclic alkyl groups; phenyl groups; alkoxyphenyl groups having 7 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 10 carbon atoms, or groups represented by the following formula (8) Indicates.
—R ¹¹ —COO—R ^{8 ′} (8)   A semiconductor integrated circuit, wherein a pattern is formed by the resist composition according to claim 1.   A pattern is formed using the resist composition as described in any one of Claims 1-7, The manufacturing method of the semiconductor integrated circuit characterized by the above-mentioned.