WO2012098952A1 - Dérivé d'ester d'acide vinylsulfonique, polymère et composition de photoréserve - Google Patents

Dérivé d'ester d'acide vinylsulfonique, polymère et composition de photoréserve Download PDF

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WO2012098952A1
WO2012098952A1 PCT/JP2012/050275 JP2012050275W WO2012098952A1 WO 2012098952 A1 WO2012098952 A1 WO 2012098952A1 JP 2012050275 W JP2012050275 W JP 2012050275W WO 2012098952 A1 WO2012098952 A1 WO 2012098952A1
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group
carbon atoms
polymer compound
photoresist composition
mol
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中山　修
佳典 谷
隆司 福本
明展 竹田
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株式会社クラレ
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/04—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
    • C07D493/18—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D497/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D497/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having oxygen and sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D497/18—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain

Definitions

  • a vinyl sulfonic acid ester derivative a polymer compound obtained by polymerizing a raw material containing the vinyl sulfonic acid ester derivative, and line width roughness (LWR) are improved to form a high-resolution resist pattern. Relates to a photoresist composition.
  • a photoresist film made of a photoresist material is formed on a substrate, and the photoresist film is selected by radiation such as light or electron beam through a mask on which a predetermined pattern is formed.
  • a photoresist material in which the exposed portion changes to a property that dissolves in the developer is referred to as a positive photoresist material
  • a photoresist material that changes to a property in which the exposed portion does not dissolve in the developer is referred to as a negative photoresist material.
  • Photoresist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions.
  • a chemically amplified photoresist composition containing a base material component whose solubility in an alkaline developer is changed by the action of an acid and an acid generator component that generates an acid upon exposure as a photoresist material that satisfies such requirements Is used.
  • a positive chemically amplified photoresist composition is generally a photoresist composition containing a resin component (base resin) whose solubility in an alkaline developer is increased by the action of an acid and an acid generator component. It is used for.
  • the photoresist composition containing the acrylic resin described in Patent Document 1 has not yet been able to satisfy the required lithography characteristics and pattern shape as the pattern becomes finer.
  • there are demands for the development of new materials that can be used for lithography applications as further progress in lithography technology and expansion of application fields are expected.
  • various lithographic properties such as resolution, line width roughness (LWR), and the like, and a photoresist material whose pattern shape is improved more than ever are desired. Therefore, the development itself of a new compound (monomer) that can be a structural unit of a polymer compound to be contained in a photoresist composition is important.
  • the present invention has been made in view of the above circumstances, and provides a novel vinyl sulfonate derivative that can be a structural unit of a polymer compound to be contained in a photoresist composition, containing the vinyl sulfonate derivative A polymer composition obtained by polymerizing a raw material to be polymerized, and a photoresist composition containing the polymer compound and having an improved LWR and forming a high-resolution photoresist pattern than before The task is to do.
  • the inventors of the present invention have a photoresist composition using a polymer compound obtained by polymerizing a raw material containing a specific vinyl sulfonate derivative having a vinylsulfonyl group as a polymerizable group. It has been found that the LWR is improved as compared with the prior art to form a high-resolution photoresist pattern.
  • R 1 represents a hydrogen atom or a methyl group.
  • W represents an alkylene group having 1 to 10 carbon atoms or a cyclic hydrocarbon group having 4 to 10 carbon atoms.
  • N represents 0 or 1.
  • A represents the following: Represents general formula (A-1), (A-2), (A-3) or (A-4); R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 3 to 3 carbon atoms.
  • R 9 and R 10 may be linked to represent —CH 2 —, —CH 2 CH 2 —, —O—, and —S—.
  • Y represents an oxygen atom or> NR 13 (R 13 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a cyclic hydrocarbon group having 3 to 10 carbon atoms which may have a substituent).
  • Z represents> C ⁇ O or> SO 2 .
  • the diffusion length of the acid generated from the photoacid generator during exposure can be controlled to be short.
  • LWR is improved and a high-resolution photoresist pattern is formed.
  • Vinyl sulfonic acid ester derivative (1) In order to obtain a photoresist composition having an improved LWR by controlling the acid diffusion length to be short, a vinyl sulfonic acid ester derivative represented by the following general formula (1) (hereinafter referred to as a vinyl sulfonic acid ester derivative (1)): .) Is useful.
  • R 1 represents a hydrogen atom or a methyl group.
  • W represents an alkylene group having 1 to 10 carbon atoms or a cyclic hydrocarbon group having 4 to 10 carbon atoms.
  • alkylene group having 1 to 10 carbon atoms represented by W include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, and propane-1,2 -Diyl group, propane-1,3-diyl group, pentane-1,5-diyl group, hexane-1,1-diyl group and the like.
  • a methylene group and an ethane-1,1-diyl group are preferable from the viewpoint of obtaining a photoresist composition in which the acid diffusion length is controlled to be short.
  • the cyclic hydrocarbon group having 4 to 10 carbon atoms represented by W is preferably a cycloalkylene group, such as a cyclohexane-1,2-diyl group, a cyclohexane-1,4-diyl group, a cyclodecane-1,5-diyl group.
  • n 0 or 1
  • n is preferably 0 from the viewpoint of obtaining a photoresist composition in which the acid diffusion length is controlled to be short.
  • A represents the following general formula (A-1), (A-2), (A-3) or (A-4).
  • Y represents an oxygen atom or NR 13
  • R 13 represents an alkyl group having 1 to 5 carbon atoms or a cyclic hydrocarbon group having 3 to 10 carbon atoms.
  • Examples of the alkyl group having 1 to 5 carbon atoms represented by R 13 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, and an isopentyl group. , S-pentyl group, t-pentyl group and the like.
  • Examples of the cyclic hydrocarbon group having 3 to 10 carbon atoms represented by R 13 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, and a bicyclo [2.2.1] heptan-1-yl group. Etc.
  • Z represents> C ⁇ O or> SO 2 .
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, carbon A cyclic hydrocarbon group having 3 to 10 carbon atoms, —COOR 12 (R 12 represents an alkyl group having 1 to 5 carbon atoms or an optionally substituted cyclic hydrocarbon group having 3 to 10 carbon atoms).
  • R 9 and R 10 may be linked to represent —CH 2 —, —CH 2 CH 2 —, —O—, —S—.
  • Examples of the alkyl group having 1 to 5 carbon atoms each independently represented by R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 include a methyl group, Examples include an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, s-pentyl group, t-pentyl group and the like.
  • Examples of the cyclic hydrocarbon group having 3 to 10 carbon atoms each independently represented by R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 include cyclo A propyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a bicyclo [2.2.1] heptan-1-yl group, and the like can be given.
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 11 each independently represents —COOR 12
  • R 12 is an alkyl group having 1 to 5 carbon atoms or a substituent.
  • the alkyl group having 1 to 5 carbon atoms represented by R 12 may be, for example, a methyl group, an ethyl group, an n-propyl group, Examples include isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, s-pentyl group, t-pentyl group and the like.
  • Examples of the cyclic hydrocarbon group having 3 to 10 carbon atoms which may have a substituent represented by R 12 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a bicyclo [2.2 .1] heptan-1-yl group, 1-methyl-1-cyclopentyl group, 1-ethyl-1-cyclopentyl group, 1-isopropyl-1-cyclopentyl group, 1-methyl-1-cyclohexyl group, 1-ethyl- Examples include 1-cyclohexyl group, 1-isopropyl-1-cyclohexyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group and the like.
  • vinyl sulfonic acid in which R 9 and R 10 are linked to represent —CH 2 —, —CH 2 CH 2 —, —O—, —S— Ester derivatives are preferred.
  • R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 and R 11 represent hydrogen atoms
  • R 4 represents a hydrogen atom or —COOR 12
  • R 12 represents an alkyl group having 1 to 5 carbon atoms or a cyclic hydrocarbon group having 3 to 10 carbon atoms which may have a substituent
  • R 9 And R 10 are connected to each other to represent —CH 2 —, —O—
  • W is a vinyl sulfonate derivative in which methylene group or ethane-1,1-diyl group is represented.
  • the vinyl sulfonate derivative (1) in which n is 0 can be produced by the following polymerizable group introduction step-A.
  • the alcohol derivative (2) and the formula CH 2 CR 1 SO 2 X 1 (wherein X 1 represents a chlorine atom, a bromine atom or an iodine atom, and R 1 represents the above definition)
  • the formula X 2 CH 2 CHR 1 SO 2 X 1 (wherein X 2 represents a chlorine atom, a bromine atom or an iodine atom, and R 1 and X 1 are as defined above).
  • the compounds shown (hereinafter these compounds are referred to as “polymerizable group introducing agent A”) are reacted in the presence of a basic substance.
  • the vinyl sulfonate derivative (1) where n is 1 can be produced by the following polymerizable group introduction step-B.
  • the polymerizable group introducing step-B includes polymerizable group introducing steps-B1 and B2.
  • X 3 and X 4 are each independently a chlorine atom, Represents a bromine atom or an iodine atom), formula (X 3 —W—CO) 2 O (wherein X 3 and W are as defined above), formula X 3 —W—COOC ( ⁇ O) R 14 (wherein X 3 and W are as defined above.
  • R 14 represents a t-butyl group or a 2,4,6-trichlorophenyl group) or a formula X 3 -W-COOSO 2 R 15 (Wherein X 3 and W are as defined above; R 15 represents a methyl group or a p-tolyl group) (hereinafter these compounds are referred to as “linking group introducing agent B1”). .)
  • linking group introducing agent B1 In the presence of a basic substance.
  • the polymerizable group introduction step-A and the polymerizable group introduction step-B will be described in order.
  • Examples of the compound represented by the formula X 2 CH 2 CHR 1 SO 2 X 1 include 2-chloroethanesulfonyl chloride, 2-bromoethanesulfonyl bromide, 2-iodoethanesulfonyl iodide and the like.
  • the amount of the polymerizable group-introducing agent A used is not particularly limited, but is preferably 0.8 to 5 mol with respect to 1 mol of the alcohol derivative (2) from the viewpoint of economy and ease of post-treatment. More preferably, it is 0.8-3 mol.
  • Examples of the basic substance used in the polymerizable group introduction step-A include alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; sodium carbonate and carbonate Alkali metal carbonates such as potassium; tertiary amines such as triethylamine, tributylamine and diazabicyclo [2.2.2] octane; nitrogen-containing heterocyclic aromatic compounds such as pyridine and 2,6-lutidine . Among these, tertiary amines and nitrogen-containing heterocyclic aromatic compounds are preferable.
  • the amount of the basic substance used is not particularly limited, but is preferably 0.8 to 10 moles per mole of the alcohol derivative (2) from the viewpoint of economy and ease of post-treatment. More preferably, it is ⁇ 6 mol.
  • the polymerizable group introduction step-A can be carried out in the presence or absence of a solvent.
  • Solvents that can be used are not particularly limited as long as they do not inhibit the reaction.
  • aliphatic hydrocarbons such as hexane, heptane, and octane
  • aromatic hydrocarbons such as toluene, xylene, and cymene
  • halogenated compounds such as methylene chloride and dichloroethane.
  • Hydrocarbons ethers such as tetrahydrofuran and diisopropyl ether
  • nitriles such as acetonitrile and benzonitrile.
  • a solvent may be used individually by 1 type, or 2 or more types may be mixed and used for it.
  • the amount used is preferably 0.1 to 20 parts by mass with respect to 1 part by mass of the alcohol derivative (2) from the viewpoint of economy and ease of post-treatment. More preferably, it is 10 parts by mass.
  • the reaction temperature of the polymerizable group introducing step-A varies depending on the type of the polymerizable group introducing agent A, the alcohol derivative (2), and the basic substance to be used, but is generally preferably ⁇ 50 to 80 ° C. Although there is no restriction
  • the polymerizable group introduction step-A is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon from the viewpoint of the yield of the vinyl sulfonate derivative (1).
  • the reaction of the polymerizable group introduction step-A can be stopped by adding water and / or alcohol.
  • Preferred examples of the alcohol include methanol, ethanol, n-propanol, and isopropanol.
  • the amount of water or alcohol used is preferably 1 mol or more per excess of polymerizable group-introducing agent A relative to 1 mol of alcohol derivative (2). If it is this usage-amount, excess polymeric group introducing agent A can be decomposed
  • Specific examples of the n 0 vinyl sulfonic acid ester derivative (1) that can be produced by the polymerizable group introduction step-A are shown below, but are not particularly limited thereto.
  • Examples of the compound represented by the formula X 3 —W—COOC ( ⁇ O) R 14 include chloroacetic acid pivalic anhydride, chloroacetic acid 2,4,6-trichlorobenzoic anhydride, 2-chloropropionic acid pivalic anhydride And 2-chloropropionic acid 2,4,6-trichlorobenzoic anhydride.
  • Examples of the compound represented by the formula X 3 —W—COOSO 2 R 15 include chloroacetic acid methanesulfonic acid anhydride, chloroacetic acid p-toluenesulfonic acid anhydride, 2-chloropropionic acid methanesulfonic acid anhydride, 2-chloro Examples include propionic acid p-toluenesulfonic acid anhydride.
  • Examples of the compound represented by the formula (X 3 -W—CO) 2 O include chloroacetic anhydride and 2-chloropropionic anhydride.
  • the amount of the linking group introducing agent B1 used is not particularly limited, but is preferably 0.8 to 5 mol with respect to 1 mol of the alcohol derivative (2) from the viewpoint of economy and ease of post-treatment. More preferably, it is 8 to 3 mol.
  • Examples of the basic substance used in the polymerizable group introducing step-B1 include the same basic substances as those used in the polymerizable group introducing step-A.
  • the amount of the basic substance used is not particularly limited, but is preferably 0.8 to 5 mol with respect to 1 mol of the alcohol derivative (2) from the viewpoint of economy and ease of post-treatment. More preferably, it is ⁇ 3 mol.
  • the polymerizable group introduction step-B1 can be carried out in the presence or absence of a solvent.
  • the solvent that can be used is not particularly limited as long as the reaction is not inhibited, and examples thereof include the same solvents that can be used in the polymerizable group introduction step-A.
  • a solvent may be used individually by 1 type, or 2 or more types may be mixed and used for it.
  • the amount used is preferably 0.1 to 20 parts by mass with respect to 1 part by mass of the alcohol derivative (2) from the viewpoint of economy and ease of post-treatment. More preferably, it is 10 parts by mass.
  • the reaction temperature in the polymerizable group introduction step -B1 varies depending on the kind of the linking group introduction agent B1, the alcohol derivative (2), and the basic substance used, but is generally preferably -50 to 80 ° C.
  • the reaction pressure in the polymerizable group introduction step-B1 is usually carried out at normal pressure.
  • the polymerizable group introduction step-B1 is preferably performed in an atmosphere of an inert gas such as nitrogen or argon from the viewpoint of the yield of the target compound.
  • the reaction of the polymerizable group introduction step-B1 can be stopped by adding water and / or alcohol.
  • Preferred examples of the alcohol include methanol, ethanol, n-propanol, and isopropanol.
  • the amount of water or alcohol used is preferably 1 mol or more per 1 mol of the alcohol derivative (2) with respect to the excess linking group introducing agent B1. With this amount, excess linking group introducing agent B1 can be completely decomposed and no by-product is produced.
  • -Polymerizable group introduction step-B2- Polymerizable group introduction step-As the polymerizable group introduction agent B2 used in B2, examples of the compound represented by the formula CH 2 CR 1 SO 3 M include sodium vinylsulfonate, potassium vinylsulfonate, triethylammonium vinylsulfonate, and the like. Is mentioned. These can be prepared by reacting vinyl sulfonic acid with a base such as sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, triethylamine in the reaction system. A method using an aqueous sodium vinyl sulfonate solution is preferred.
  • the amount of the polymerizable group-introducing agent B2 used is preferably 0.8 to 10 mol with respect to 1 mol of the product of the polymerizable group-introducing step-B1, from the viewpoint of economy and ease of post-treatment. More preferably, it is 0.8 to 5 mol.
  • the amount used is preferably 0.001 to 0.5 mol with respect to 1 mol of the product of the polymerizable group introduction step-B1. From the viewpoint, it is more preferably 0.005 to 0.3 mol.
  • the polymerizable group introduction step-B2 can be carried out in the presence or absence of a solvent.
  • Solvents that can be used are not particularly limited as long as they do not inhibit the reaction.
  • aliphatic hydrocarbons such as hexane, heptane, and octane
  • aromatic hydrocarbons such as toluene, xylene, and cymene
  • methanol, ethanol, 1-propanol examples include alcohols such as 2-propanol; halogenated hydrocarbons such as methylene chloride and dichloroethane; ethers such as tetrahydrofuran and diisopropyl ether; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.
  • a solvent may be used individually by 1 type, or 2 or more types may be mixed and used for it.
  • the amount used is 0.1 to 20 parts by mass with respect to 1 part by mass of the product of the polymerizable group introduction step-B1 from the viewpoint of economy and ease of post-treatment.
  • the amount is preferably 0.1 to 10 parts by mass.
  • the reaction temperature of the polymerizable group introduction step-B2 varies depending on the polymerizable group introduction agent B2 used, the product of the polymerizable group introduction step-B1, and the type of basic substance, but is generally -50 to 80 ° C. It is preferable. Although there is no restriction
  • limiting in particular in reaction pressure, Usually, reaction is implemented at a normal pressure. Specific examples of the vinyl sulfonic acid ester derivative (1) with n 1 that can be produced by the polymerizable group introduction step-B are shown below, but are not particularly limited thereto.
  • the vinyl sulfonic acid ester derivative (1) obtained through the polymerizable group introduction step-A or the polymerizable group introduction step-B is preferably separated and purified by a conventional method as necessary.
  • the reaction mixture obtained in the polymerizable group introduction step-A or the polymerizable group introduction step-B is washed with water, concentrated, and used for separation and purification of ordinary organic compounds such as distillation, column chromatography or recrystallization. Can be separated and purified by the method described.
  • metals such as filtration or zetaplus (trade name, manufactured by Cuno Co., Ltd.) and protego (product name, manufactured by Nihon Microlith Co., Ltd.) It is also possible to reduce the metal content in the obtained vinyl sulfonate derivative (1) by treating with a removal filter.
  • the alcohol derivative (2) as a raw material includes a commercially available compound, and can be produced by a method disclosed in patent documents and non-patent documents.
  • a polymer obtained by polymerizing the vinyl sulfonic acid ester derivative (1) of the present invention alone or a copolymer obtained by copolymerizing the vinyl sulfonic acid ester derivative (1) with another polymerizable compound is a photoresist composition. It is useful as a polymer compound for physical use.
  • the polymer compound of the present invention contains more than 0 mol% and 100 mol% of the structural unit based on the vinyl sulfonate derivative (1), and is preferably 5 to 80 mol% from the viewpoint of LWR and resolution. The content is preferably 10 to 70 mol%, more preferably 10 to 50 mol%.
  • copolymerization monomers examples include, for example, compounds represented by the following chemical formulas. However, it is not particularly limited to these.
  • R 16 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a cyclic hydrocarbon group having 3 to 10 carbon atoms
  • R 17 represents a polymerizable group
  • R 18 represents a hydrogen atom or —COOR 19 (R 19 represents an alkyl group having 1 to 3 carbon atoms).
  • m represents an integer of 1 to 4.
  • examples of the alkyl group having 1 to 5 carbon atoms represented by R 16 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, Examples include an isopentyl group and an s-pentyl group.
  • examples of the cyclic hydrocarbon group having 3 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • Examples of the polymerizable group represented by R 17 include an acryloyl group, a methacryloyl group, a vinyl group, and a vinylsulfonyl group.
  • examples of the alkyl group having 1 to 3 carbon atoms represented by R 19 include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • the copolymerization monomer is preferably a copolymerization monomer represented by the above formula (I), (II), (IV), (V), (VII), (VIII) or (IX).
  • a comonomer represented by formula (I), a comonomer represented by (II), and a comonomer represented by (IX) It is combined use with.
  • the polymer compound can be produced by radical polymerization according to a conventional method.
  • a method for synthesizing a polymer compound having a small molecular weight distribution includes living radical polymerization.
  • a general radical polymerization method includes a radical polymerization initiator and a solvent as well as one or more kinds of vinyl sulfonic acid ester derivatives (1) and, if necessary, one or more kinds of the above-mentioned copolymerization monomers as necessary. And polymerizing in the presence of a chain transfer agent.
  • radical polymerization there is no restriction
  • the usual method used when manufacturing acrylic resin such as solution polymerization method, emulsion polymerization method, suspension polymerization method, block polymerization method, etc. can be used.
  • radical polymerization initiator examples include hydroperoxide compounds such as t-butyl hydroperoxide and cumene hydroperoxide; di-t-butyl peroxide, t-butyl- ⁇ -cumyl peroxide, di- ⁇ -cumyl peroxide and the like.
  • examples thereof include dialkyl peroxide compounds; diacyl peroxide compounds such as benzoyl peroxide and diisobutyryl peroxide; azo compounds such as 2,2′-azobisisobutyronitrile and dimethyl-2,2′-azobisisobutyrate.
  • the amount of radical polymerization initiator used is appropriately selected according to the polymerization conditions such as the vinyl sulfonate derivative (1), copolymerization monomer, chain transfer agent, solvent used and the polymerization temperature used in the polymerization reaction.
  • the amount is usually preferably 0.005 to 0.2 mol, more preferably 0.01 to 0.15 mol per 1 mol.
  • the solvent is not particularly limited as long as the polymerization reaction is not inhibited.
  • propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether propionate, ethylene Glycol ethers such as glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether; esters such as ethyl lactate, methyl 3-methoxypropionate, methyl acetate, ethyl acetate, propyl acetate; acetone, methyl ethyl ketone, methyl ipropyl ketone, methyl isobutyl Ketone, methyl amyl ketone, cyclopentanone, cyclohexano Ketones, such as diethyl ether, diisopropyl ether, dibutyl ether
  • chain transfer agent examples include thiol compounds such as dodecanethiol, mercaptoethanol, mercaptopropanol, mercaptoacetic acid, and mercaptopropionic acid.
  • the amount used is usually preferably 0.005 to 0.2 mol, more preferably 0.01 to 0.15 mol, per 1 mol of all polymerizable compounds.
  • the polymerization temperature is usually preferably 40 to 150 ° C., and more preferably 60 to 120 ° C. from the viewpoint of the stability of the polymer compound produced.
  • the polymerization reaction time varies depending on the polymerization conditions such as the vinyl sulfonic acid ester derivative (1), the comonomer, the polymerization initiator, the type and amount of the solvent used, and the temperature of the polymerization reaction, but is usually preferably 30 minutes. 48 hours, more preferably 1 to 24 hours.
  • the polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon.
  • the polymer compound thus obtained can be isolated by ordinary operations such as reprecipitation.
  • the isolated polymer compound can be dried by vacuum drying or the like.
  • the solvent used in the reprecipitation operation include aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene and xylene; methylene chloride, chloroform, chlorobenzene, dichlorobenzene, and the like.
  • Nitrogenated hydrocarbons such as nitromethane; Nitriles such as acetonitrile and benzonitrile; Ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and 1,4-dioxane; Ketones such as acetone and methyl ethyl ketone; Carboxyls such as acetic acid Acid; Esters such as ethyl acetate and butyl acetate; Carbonates such as dimethyl carbonate, diethyl carbonate, and ethylene carbonate; Methanol, ethanol, propanol, isopropyl alcohol Include water; alcohols such as butanol.
  • the amount of solvent used in the reprecipitation operation varies depending on the type of polymer compound and the type of solvent, but it is usually preferably 0.5 to 100 parts by mass with respect to 1 part by mass of the polymer compound. From the viewpoint of properties, the amount is more preferably 1 to 50 parts by mass.
  • the weight average molecular weight (Mw) of the polymer compound is not particularly limited, but is preferably 500 to 50,000, more preferably 1,000 to 30,000, still more preferably 5,000 to 15,000.
  • the utility as a component of the photoresist composition mentioned later is high.
  • Mw is a value measured according to the method described in Examples.
  • the molecular weight distribution (Mw / Mn) of the polymer compound is not particularly limited, but is preferably 1.0 to 3, more preferably 1.0 to 2.0. It is highly useful.
  • Mw and Mn are values measured according to the method described in Examples.
  • the photoresist composition of the present invention is prepared by blending a pre-polymer compound, a photoacid generator and a solvent, and if necessary, a basic compound, a surfactant and other additives.
  • a pre-polymer compound e.g., ethylene glycol dimethacrylate copolymer compound
  • a photoacid generator e.g., ethylene glycol dimethacrylate copolymer
  • a solvent e.g., ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate,
  • Photoacid generator There is no restriction
  • the photoacid generator include onium salt photoacid generators such as iodonium salts and sulfonium salts; oxime sulfonate photoacid generators; bisalkyl or bisarylsulfonyldiazomethane photoacid generators; nitrobenzyl sulfonate photons. Examples include acid generators; iminosulfonate photoacid generators; disulfone photoacid generators. You may use these individually by 1 type or in mixture of 2 or more types.
  • an onium salt-based photoacid generator is preferable, and the following fluorine-containing onium salt containing a fluorine-containing alkylsulfonic acid ion as an anion is preferable from the viewpoint that the strength of the generated acid is strong.
  • fluorine-containing onium salt examples include, for example, diphenyliodonium trifluoromethanesulfonate or nonafluorobutanesulfonate; bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate or nonafluorobutanesulfonate; triphenylsulfonium trifluoromethane.
  • the blending amount of the photoacid generator is usually preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the polymer compound from the viewpoint of ensuring the sensitivity and developability of the photoresist composition. 0.5 to 10 parts by mass.
  • Solvents to be blended in the photoresist composition include, for example, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether propionate, ethylene glycol monobutyl ether, ethylene glycol Glycol ethers such as monobutyl ether acetate and diethylene glycol dimethyl ether; esters such as ethyl lactate, methyl 3-methoxypropionate, methyl acetate, ethyl acetate, and propyl acetate; acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclo Ketones such as pentanone and cyclohexanone Diethyl ether, diisopropyl ether, dibutyl ether, di
  • a basic compound is added to the photoresist composition in an amount that does not impair the characteristics of the photoresist composition as necessary. be able to.
  • Examples of such basic compounds include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N- (1-adamantyl) acetamide, benzamide, N-acetyl.
  • the blending amount varies depending on the type of the basic compound used, but is usually preferably 0.01 to 10 moles, more preferably 0.05 to 1 mole of the photoacid generator. ⁇ 1 mole.
  • the photoresist composition may further contain a surfactant in an amount that does not impair the characteristics of the photoresist composition, if desired.
  • a surfactant examples include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, and the like. These may be used individually by 1 type and may use 2 or more types together.
  • the surfactant is blended, the blending amount is usually preferably 2 parts by mass or less with respect to 100 parts by mass of the polymer compound.
  • a sensitizer As other additives, a sensitizer, an antihalation agent, a shape improver, a storage stabilizer, an antifoaming agent, etc. are added in an amount that does not impair the characteristics of the photoresist composition. Can be blended.
  • a photoresist composition is applied to a substrate, pre-baked usually at 70 to 160 ° C. for 1 to 10 minutes, irradiated with radiation through a predetermined mask (exposure), and preferably 1 to 5 at 70 to 160 ° C.
  • a predetermined photoresist pattern can be formed by post-exposure baking for a minute to form a latent image pattern and then developing with a developer.
  • Exposure is preferably from 0.1 ⁇ 1000mJ / cm 2, and more preferably 1 ⁇ 500mJ / cm 2.
  • the developer examples include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate and aqueous ammonia; alkylamines such as ethylamine, diethylamine and triethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxy And an alkaline aqueous solution in which a quaternary ammonium salt such as tetraethylammonium hydroxide is dissolved.
  • a quaternary ammonium salt such as tetraethylammonium hydroxide or tetraethylammonium hydroxide is dissolved.
  • concentration of the developer is usually preferably from 0.1 to 20% by mass, and more preferably from 0.1 to 10% by mass.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) using a differential refractometer as a detector and tetrahydrofuran (THF) as an eluent under the following conditions. It calculated
  • GPC measurement As a column, three “TSK-gel supermultipore HZ-M” (trade name: 4.6 mm ⁇ 150 mm, manufactured by Tosoh Corporation) connected in series, a column temperature of 40 ° C., a differential refractometer The measurement was performed under the conditions of a temperature of 40 ° C. and an eluent flow rate of 0.35 mL / min.
  • aqueous solution (A) This aqueous solution is referred to as “aqueous solution (A)”. All of the “aqueous solution (A)” was placed in a three-necked flask having an internal volume of 3 L equipped with a stirrer and a thermometer, and cooled to 10 ° C. After dropping 93.27 g (2.01 mol) of 99% formic acid at an internal temperature of 11 to 15 ° C. and heating to an internal temperature of 50 to 53 ° C., 162.50 g (1. 43 mol) was added dropwise over 3 hours. The internal temperature was maintained at around 50 ° C. even after the completion of the dropwise addition, and the reaction mixture was analyzed by HPLC 17 hours after the completion of the dropwise addition.
  • the reaction mixture was stirred at an internal temperature of ⁇ 60 ° C. for 5 minutes, then heated to 25 ° C. and stirred for 45 minutes. Next, the internal temperature was cooled to 5 ° C., and 20 mL of 1% sulfuric acid aqueous solution was added. Subsequently, the organic layer obtained by liquid separation was washed with 20 mL of water, and then the organic layer was washed with a 20% aqueous sodium chloride solution. Sodium sulfate was added to the resulting organic layer for drying and filtration. The filtrate was concentrated under reduced pressure to obtain 19 g of black oil. This oil was subjected to simple distillation under the conditions of 13.3 Pa and 45 ° C. to obtain 14.35 g (purity 97.3%, 0.11 mol) of vinyl chlorosulfone having the following structure (yield 69.6%). .
  • Example 5 Preparation of tetrahydro-2-oxo-3-furanyl vinyl sulfonate 2-hydroxy-4-oxa-5-thiatricyclo [4.2.1.0 3,7 ] nonane-5,5-dioxide
  • the same procedure as in Example 1 was performed except that 1.3 g (12.7 mmol) of 3-hydroxytetrahydro-2-oxofuran was used instead of 2.4 g (12.7 mmol), and tetrahydro-2 having the following characteristics was obtained.
  • 1.8 g (9.4 mmol) of -oxo-3-furanyl vinyl sulfonate was obtained (74% yield).
  • 3-hydroxyadamantan-1-yl methacrylate 1.3 g (5.6 mmol), 2-vinylsulfonyloxy-4-oxa-5-thiatricyclo [4.2.1.0 3,7 ] nonane-5 , 5-dioxide (5.4 g, 19.4 mmol) and methyl ethyl ketone (36.4 g) were charged, and nitrogen bubbling was performed for 10 minutes. Under a nitrogen atmosphere, 0.36 g (2 mmol) of 2,2′-azobisisobutyronitrile was charged, and a polymerization reaction was performed at 80 ° C. for 4 hours.
  • the obtained reaction mixture was added dropwise to 220 g of methanol at room temperature while stirring, and the resulting precipitate was collected by filtration.
  • the precipitate was dried under reduced pressure (26.7 Pa) at 50 ° C. for 7 hours to obtain 7.3 g of a polymer compound (a) composed of the following repeating units (the numerical values represent molar ratios).
  • the weight average molecular weight (Mw) of the obtained polymer compound (a) was 8900, and the molecular weight distribution was 1.9.
  • Mw weight average molecular weight
  • Example 8 Synthesis of Polymer Compound (c) 2-vinylsulfonyloxy-4-oxa-5-thiatricyclo [4.2.1.0 3,7 ] nonane-5,5-dioxide 5.4 g (19 Instead of 4-vinylsulfonyloxy-4,8-dioxa-5-thiatricyclo [4.2.1.0 3,7 ] nonane-5,5-dioxide 5.5 g (19.4 mmol) Except that it was used, the same operation as in Example 6 was performed to obtain 7.1 g of a polymer compound (c) composed of the following repeating units (the numerical value represents a molar ratio). The obtained polymer compound (c) had a weight average molecular weight (Mw) of 9,200 and a molecular weight distribution of 1.9.
  • Mw weight average molecular weight
  • Mw weight average molecular weight
  • Mw weight average molecular weight
  • photoresist compositions were filtered using a membrane filter having a pore size of 0.2 ⁇ m.
  • a cresol novolak resin ("PS-6937" manufactured by Gunei Chemical Industry Co., Ltd.) was applied with a 6% by mass propylene glycol monomethyl ether acetate solution by spin coating, and baked on a hot plate at 200 ° C for 90 seconds.
  • Each of the filtrates was applied by spin coating on a silicon wafer having a diameter of 10 cm on which an antireflection film (underlayer film) having a thickness of 100 nm was formed, and pre-baked on a hot plate at 130 ° C. for 90 seconds to have a thickness of 300 nm.
  • a photoresist film was formed.
  • This photoresist film was exposed by a two-beam interference method using an ArF excimer laser having a wavelength of 193 nm. Subsequently, the film was post-exposure baked at 130 ° C. for 90 seconds, and then developed with a 2.38% by mass-tetramethylammonium hydroxide aqueous solution for 60 seconds to form a 1: 1 line and space pattern.
  • the developed wafer was cleaved and observed with a scanning electron microscope (SEM), and the pattern shape observation and line width variation (hereinafter referred to as LWR) at an exposure amount obtained by resolving a line and space with a line width of 100 nm at 1: 1. Measured).
  • SEM scanning electron microscope
  • the line width is detected at a plurality of positions in the measurement monitor, and the dispersion (3 ⁇ ) of variations in the detected positions is used as an index.
  • the cross-sectional shape of the pattern is observed using a scanning electron microscope (SEM), and the pattern having a high rectangularity (close to a rectangle) is defined as “good”, and a T-top or microbridge is formed. Those with low shortness were evaluated as “bad”. The results are shown in Tables 1 and 2.
  • the photoresist composition of the present invention is useful in the production of semiconductors and printed boards because the LWR is improved and a high-resolution photoresist pattern is formed.

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Abstract

Cette invention concerne une composition de photoréserve qui comprend un polymère qui contient un dérivé d'ester d'acide vinylsulfonique spécifique à titre de motifs constitutifs et qui présente un LWR amélioré et peut produire un motif à haute résolution. Le dérivé d'ester d'acide vinylsulfonique spécifique selon l'invention est représenté par la formule (1). [Dans la formule (1), R1 est un atome d'hydrogène ou un méthyle ; W est un alkylène ou un groupe hydrocarbure cyclique ; n vaut de 0 à 1 ; et A est un groupe représenté par l'une quelconque des formules (A-1) à (A-4) suivantes [où R2 à R11 sont chacun indépendamment un atome d'hydrogène, un groupe alkyle, hydrocarbure cyclique, ou autre groupe similaire ; R9 et R10 peuvent ensemble représenter -CH2-, -CH2CH2-, -O-, ou -S- ; Y est un atome d'oxygène ou >NR13 (où R13 est un atome d'hydrogène, un groupe alkyle ou autre groupe similaire) ; et Z est >C=O ou >SO2]].
PCT/JP2012/050275 2011-01-17 2012-01-10 Dérivé d'ester d'acide vinylsulfonique, polymère et composition de photoréserve WO2012098952A1 (fr)

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JP2012190013A (ja) * 2011-02-25 2012-10-04 Sumitomo Chemical Co Ltd レジスト組成物及びレジストパターンの製造方法
WO2013129342A1 (fr) * 2012-02-27 2013-09-06 株式会社クラレ Dérivé d'ester d'acide acrylique et son procédé de production, intermédiaire et son procédé de production, composé de poids moléculaire élevé et composition de résine photosensible
WO2015045240A1 (fr) * 2013-09-24 2015-04-02 International Business Machines Corporation Polymères contenant un ester d'acide sulfonique et destinés à des résines photosensibles à deux tons à base de solvant organique
JP2016071207A (ja) * 2014-09-30 2016-05-09 Jsr株式会社 感放射線性樹脂組成物、レジストパターン形成方法、重合体及び化合物
JP2016071206A (ja) * 2014-09-30 2016-05-09 Jsr株式会社 感放射線性樹脂組成物、レジストパターン形成方法、重合体及び化合物
WO2016141563A1 (fr) * 2015-03-11 2016-09-15 株式会社大赛璐 Époxyde alicyclique et procédé de préparation correspondant, et procédé de préparation de dérivé 2-hydroxyl-4-oxa-5-thia tricycle[4.2.1.03,7] nonane

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Cited By (10)

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Publication number Priority date Publication date Assignee Title
JP2012190013A (ja) * 2011-02-25 2012-10-04 Sumitomo Chemical Co Ltd レジスト組成物及びレジストパターンの製造方法
WO2013129342A1 (fr) * 2012-02-27 2013-09-06 株式会社クラレ Dérivé d'ester d'acide acrylique et son procédé de production, intermédiaire et son procédé de production, composé de poids moléculaire élevé et composition de résine photosensible
US9395625B2 (en) 2012-02-27 2016-07-19 Kuraray Co., Ltd. Acrylic acid ester derivative and method for producing same, intermediate and method for producing same, high-molecular-weight compound, and photoresist composition
WO2015045240A1 (fr) * 2013-09-24 2015-04-02 International Business Machines Corporation Polymères contenant un ester d'acide sulfonique et destinés à des résines photosensibles à deux tons à base de solvant organique
EP3049868A1 (fr) * 2013-09-24 2016-08-03 International Business Machines Corporation Polymères contenant un ester d'acide sulfonique et destinés à des résines photosensibles à deux tons à base de solvant organique
EP3049868A4 (fr) * 2013-09-24 2017-05-10 International Business Machines Corporation Polymères contenant un ester d'acide sulfonique et destinés à des résines photosensibles à deux tons à base de solvant organique
US9772558B2 (en) 2013-09-24 2017-09-26 International Business Machines Corporation Sulfonic acid ester containing polymers for organic solvent based dual-tone photoresists
JP2016071207A (ja) * 2014-09-30 2016-05-09 Jsr株式会社 感放射線性樹脂組成物、レジストパターン形成方法、重合体及び化合物
JP2016071206A (ja) * 2014-09-30 2016-05-09 Jsr株式会社 感放射線性樹脂組成物、レジストパターン形成方法、重合体及び化合物
WO2016141563A1 (fr) * 2015-03-11 2016-09-15 株式会社大赛璐 Époxyde alicyclique et procédé de préparation correspondant, et procédé de préparation de dérivé 2-hydroxyl-4-oxa-5-thia tricycle[4.2.1.03,7] nonane

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