WO2011040175A1 - 重合体及び感放射線性組成物並びに単量体及びその製造方法 - Google Patents
重合体及び感放射線性組成物並びに単量体及びその製造方法 Download PDFInfo
- Publication number
- WO2011040175A1 WO2011040175A1 PCT/JP2010/065066 JP2010065066W WO2011040175A1 WO 2011040175 A1 WO2011040175 A1 WO 2011040175A1 JP 2010065066 W JP2010065066 W JP 2010065066W WO 2011040175 A1 WO2011040175 A1 WO 2011040175A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- polymer
- general formula
- atom
- carbon atoms
- Prior art date
Links
- 0 CC(C)c1cc(S(C)C)c(*)c(C(C)C)c1 Chemical compound CC(C)c1cc(S(C)C)c(*)c(C(C)C)c1 0.000 description 13
- WLOQLWBIJZDHET-UHFFFAOYSA-N c(cc1)ccc1[S+](c1ccccc1)c1ccccc1 Chemical compound c(cc1)ccc1[S+](c1ccccc1)c1ccccc1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 3
- AZTLFCORVZUQBD-UHFFFAOYSA-N Cc1cc(S2c3ccccc3-c3c2cccc3)cc(C)c1O Chemical compound Cc1cc(S2c3ccccc3-c3c2cccc3)cc(C)c1O AZTLFCORVZUQBD-UHFFFAOYSA-N 0.000 description 1
- UVFIXEGOSUKAPD-UHFFFAOYSA-N FC(F)(F)[S+]1c(cccc2)c2-c2c1cccc2 Chemical compound FC(F)(F)[S+]1c(cccc2)c2-c2c1cccc2 UVFIXEGOSUKAPD-UHFFFAOYSA-N 0.000 description 1
- GGMPISPXDJJENY-UHFFFAOYSA-N O=S(C(F)(F)F)(C(S(C(F)(F)F)(=O)=O)=[S](C(F)(F)F)(=O)=O)=O Chemical compound O=S(C(F)(F)F)(C(S(C(F)(F)F)(=O)=O)=[S](C(F)(F)F)(=O)=O)=O GGMPISPXDJJENY-UHFFFAOYSA-N 0.000 description 1
- GAWIEIXOIRHDMK-UHFFFAOYSA-N O=S(C(F)(F)F)([N-]S(C(F)(F)F)(=O)=[O]c1ccccc1[S+](c1ccccc1)c1ccccc1)=O Chemical compound O=S(C(F)(F)F)([N-]S(C(F)(F)F)(=O)=[O]c1ccccc1[S+](c1ccccc1)c1ccccc1)=O GAWIEIXOIRHDMK-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
-
- 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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
-
- 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
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
Definitions
- the present invention relates to a polymer, a radiation-sensitive composition using the polymer as an acid-dissociable group-containing polymer, a monomer, and a method for producing the monomer. More specifically, the present invention relates to various types of radiation such as KrF excimer lasers, ArF excimer lasers, F 2 excimer lasers, (ultra) far ultraviolet rays such as EUV, X-rays such as synchrotron radiation, and charged particle beams such as electron beams.
- the present invention relates to a radiation-sensitive composition and a polymer used as a chemically amplified resist suitable for microfabrication by the method, a monomer, and a method for producing the same.
- Lithography using an electron beam or EUV light is positioned as a next-generation or next-generation pattern forming technology, and a positive resist with high sensitivity and high resolution is desired.
- high sensitivity is a very important issue for shortening the wafer processing time.
- nano edge roughness is designed when the pattern is viewed from directly above because the resist pattern and the edge of the substrate interface vary irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. This refers to the deviation that occurs between the dimensions and the actual pattern dimensions.
- lithography using KrF excimer laser light it is also important to satisfy high sensitivity, high resolution, good pattern shape, and good nano edge roughness at the same time. is necessary.
- a resist suitable for a lithography process using KrF excimer laser light, electron beam, or EUV light a chemically amplified resist mainly utilizing an acid-catalyzed reaction is used from the viewpoint of high sensitivity.
- a phenolic polymer (hereinafter referred to as “phenolic acid-decomposable polymer”), which is insoluble or sparingly soluble in an aqueous alkali solution and becomes soluble in an aqueous alkaline solution by the action of an acid, and an acid A chemically amplified resist composition comprising a generator is effectively used.
- positive resists compounds that generate sulfonic acid upon irradiation with actinic rays or radiation using a phenolic acid-decomposable polymer copolymerized with an acid-decomposable acrylate monomer (hereinafter referred to as “sulfonic acid generator”)
- sulfonic acid generator a phenolic acid-decomposable polymer copolymerized with an acid-decomposable acrylate monomer
- the present invention has been made in view of the above circumstances, and is effectively sensitive to X-rays such as KrF excimer laser, ArF excimer laser, EUV (extreme) deep ultraviolet rays, synchrotron radiation, and electron beams, and nanoedges.
- the purpose is to provide.
- the present invention is shown below. 1.
- the polymer characterized by including the repeating unit represented by following General formula (1).
- R 1 is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group
- R 2 is a substituted or unsubstituted aryl group having 6 to 22 carbon atoms
- Y is a carbon atom
- X is an atomic group necessary for forming a cyclic structure containing a hetero atom together with Y, and represents —X 1 Z 1 X 2 —, where Z 1 represents —O—, —S—, —CO—, — COO—, —SO— or —SO 2 —, wherein X 1 and X 2 are the same or different from each other and are a single bond, a methylene group or an alkylene group having 2 to 25 carbon atoms, and X 1 and X 2 May have a substituent, and X 1 and X 2 may be bonded to
- n is an integer of 0 to 3
- R 1 is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group
- R 3 is a monovalent organic group, a hydroxyl group or a halogen atom
- Y is a carbon atom
- X is an atomic group necessary for forming a cyclic structure containing a hetero atom together with Y, and represents —X 1 Z 1 X 2 —, where Z 1 represents —O—, —S—, —CO—, — COO—, —SO— or —SO 2 —, wherein X 1 and X 2 are the same or different from each other and are a single bond, a methylene group or an alkylene group having 2 to 25 carbon atoms, and X 1 and X 2 May have
- R 4 is a hydrogen atom or a methyl group
- R 5 is a hydrogen atom or a monovalent organic group
- i is an integer of 0 to 3
- j is an integer of 0 to 3
- ⁇ i + j ⁇ 5
- R 6 is a hydrogen atom or a methyl group
- R 7 is a hydrogen atom or a monovalent organic group
- k is an integer of 0 to 3
- l is an integer of 0 to 3
- R 8 is a hydrogen atom or a methyl group
- R 9 is a hydrogen atom or a monovalent organic group
- m is an integer of 0 to 3
- n is an integer of 0 to 3, and 0 ⁇ m + n ⁇ 5 .
- R 10 is a hydrogen atom or a methyl group
- R 11 is a hydrogen atom or a monovalent organic group
- r is an integer of 0 to 3
- R 14 and R 15 are each independently an alkyl group having 1 to 20 carbon atoms substituted with at least one fluorine atom, or R 14 and R 15 Are bonded to each other to form a cyclic structure having 1 to 20 carbon atoms substituted with at least one fluorine atom, wherein R 16 , R 17 and R 18 are Independently an alkyl group having 1 to 20 carbon atoms substituted with at least one fluorine atom, or any two of R 16 , R 17 and R 18 are bonded to each other to form at least one A cyclic structure having 1 to 20 carbon atoms substituted with a fluorine atom is formed, and the remaining one is an alkyl group having 1 to 20 carbon atoms substituted with at least one fluorine atom.) 6).
- R 1 is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group
- R 2 is a substituted or unsubstituted aryl group having 6 to 22 carbon atoms
- Y is a carbon atom
- X is an atomic group necessary for forming a cyclic structure containing a hetero atom together with Y, and represents —X 1 Z 1 X 2 —, where Z 1 represents —O—, —S—, —CO—, — COO—, —SO— or —SO 2 —, wherein X 1 and X 2 are the same or different from each other and are a single bond, a methylene group or an alkylene group having 2 to 25 carbon atoms, and X 1 and X 2 May have a substituent, and X 1 and X 2 may be bonded to each other via a divalent group.
- the polymer of the present invention is suitable as an acid-dissociable group-containing polymer in a radiation-sensitive composition because it is insoluble in alkali or hardly soluble in alkali and becomes easily soluble in alkali by the action of an acid.
- a radiation sensitive composition of the present invention KrF excimer laser, ArF excimer laser, EUV and other (extreme) far ultraviolet rays, synchrotron radiation and other X-rays and electron beams are effectively sensitive to nano edge roughness and sensitivity.
- the monomer of this invention can form the polymer of the said invention suitably.
- polymer (I) includes a repeating unit represented by the following general formula (1) (hereinafter referred to as “repeating unit (1)”).
- R 1 is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group
- R 2 is a substituted or unsubstituted aryl group having 6 to 22 carbon atoms
- Y is a carbon atom
- X is an atomic group necessary for forming a cyclic structure containing a hetero atom together with Y, and represents —X 1 Z 1 X 2 —, where Z 1 represents —O—, —S—, —CO—, — COO—, —SO— or —SO 2 —, wherein X 1 and X 2 are the same or different from each other and are a single bond, a methylene group or an alkylene group having 2 to 25 carbon atoms, and X 1 and X 2 May have a substituent, and X 1 and X 2 may be bonded to each other through a divalent group.
- Y is a carbon atom, and R 2 is bonded to this carbon atom.
- R 2 is a substituted or unsubstituted aryl group having 6 to 22 carbon atoms, and can be a group derived from the following structures (x-1) to (x-3).
- R 2 is a group derived from the following (x-2) (namely, naphthyl group)
- the bonding positions bonded to Y (carbon atom) in the general formula (1) are the 1-position and 2-position. Any of these may be used.
- R 2 is a group derived from the following (x-3) (that is, an anthryl group)
- the bonding positions bonded to Y (carbon atom) in the general formula (1) are the 1-position, 2-position And 9th position.
- the following (x-1) to (x-3) show an unsubstituted structure, but may have a substituent.
- substituents include methyl group, ethyl group, propyl group, hydroxyl group, carboxyl group, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.) ), An alkyloxycarbonyl group and the like.
- X is an atomic group necessary for forming a cyclic structure containing a hetero atom together with Y (carbon atom).
- the number of carbon atoms in the cyclic structure formed by X together with Y (carbon atom) is preferably 5 to 25, more preferably 5 to 20, and still more preferably 5 to 15.
- X represents —X 1 Z 1 X 2 —, and Z 1 represents —O—, —S—, —CO—, —COO—, —SO— or —SO 2 —.
- X 1 and X 2 are the same or different from each other, a single bond, an alkylene group of a methylene group or a carbon atoms 2 ⁇ 25, X 1 and X 2 may have a substituent, X 1 And X 2 may be bonded to each other via a divalent group.
- X 1 and / or X 2 has a substituent
- substituents include a methyl group, an ethyl group, a propyl group, a hydroxyl group, a carboxyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkoxy Groups (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), alkyloxycarbonyl groups and the like.
- X 1 and X 2 are preferably a methylene group and an ethylene group.
- repeating unit (1) examples include a repeating unit represented by the following general formula (1-1) (hereinafter referred to as “repeating unit (1-1)”).
- R 1 is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group
- R 3 is a monovalent organic group, a hydroxyl group or a halogen atom
- Y is a carbon atom
- X is an atomic group necessary for forming a cyclic structure containing a hetero atom together with Y, and represents —X 1 Z 1 X 2 —, where Z 1 represents —O—, —S —, —CO—, —COO—, —SO— or —SO 2 —, wherein X 1 and X 2 are the same or different from each other, and are a single bond, a methylene group or an alkylene group having 2 to 25 carbon atoms.
- X 1 and X 2 may
- n is an integer of 0 to 3, preferably 0 to 1.
- R 3 in the general formula (1-1) is a monovalent organic group, a hydroxyl group or a halogen atom.
- Monovalent organic groups include methyl, ethyl, propyl, carboxyl, halogen atoms (fluorine, bromine, etc.), alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.), alkyloxy A carbonyl group etc. are mentioned. Of these, a methyl group, an ethyl group, and a propyl group are preferable.
- the plurality of R 3 may be the same as or different from each other.
- the repeating unit (1-1) is exemplified by the following general formulas (1-1-1) to (1-1-22).
- R 1 is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group
- R 3 is a monovalent organic group, a hydroxyl group or a halogen atom
- n is an integer of 0 to 3.
- the said repeating unit (1) can be formed by using the compound (monomer of this invention) represented by the following general formula (10) as a monomer, for example.
- R 1 is a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group
- R 2 is a substituted or unsubstituted aryl group having 6 to 22 carbon atoms
- Y is a carbon atom
- X is an atomic group necessary for forming a cyclic structure containing a hetero atom together with Y, and represents —X 1 Z 1 X 2 —, where Z 1 represents —O—, —S—, —CO—, — COO—, —SO— or —SO 2 —, wherein X 1 and X 2 are the same or different from each other and are a single bond, a methylene group or an alkylene group having 2 to 25 carbon atoms, and X 1 and X 2 May have a substituent, and X
- the compound represented by the general formula (10) (monomer of the present invention) is CH 2 ⁇ C (R 1 ) C ( ⁇ O) X (wherein R 1 is a hydrogen atom, a methyl group, a fluorine atom) Or a trifluoromethyl group and X is a halogen atom.) And a compound that can be subjected to a substitution reaction with X in the compound can be produced. .
- the following is a production example of the compound (1-1-1a) capable of forming the repeating unit represented by the general formula (1-1-1), and the compound (1-1-1a) has the following general formula: It can be produced by reacting a compound represented by (1-r1) with a compound represented by the following general formula (1-r2).
- the polymer (I) of the present invention is a polymer containing the repeating unit (1). Therefore, this polymer (I) may be composed only of the repeating unit (1), but in addition to the repeating unit (1), the repeating unit represented by the following general formula (2) (hereinafter, "Repeating unit (2)”), a repeating unit represented by the following general formula (3) (hereinafter referred to as “repeating unit (3)”), a repeating unit represented by the following general formula (4) ( Hereinafter, it is referred to as “repeating unit (4)”), a repeating unit represented by the following general formula (5) (hereinafter referred to as “repeating unit (5)”), and represented by the following general formula (N).
- the repeating unit represented by the following general formula (2) hereinafter, "Repeating unit (2)
- a repeating unit represented by the following general formula (3) hereinafter referred to as “repeating unit (3)
- a repeating unit represented by the following general formula (4) hereinafter, it is referred to as “re
- repeating unit (N) At least one of repeating units (hereinafter referred to as “repeating unit (N)”) may be further included.
- the lower limit of the content of the repeating unit (1) in the polymer (I) of the present invention is preferably 1 mol% when the total of repeating units constituting the polymer (I) is 100 mol%. More preferably, it is 5 mol%, still more preferably 10 mol%.
- R 4 is a hydrogen atom or a methyl group
- R 5 is a hydrogen atom or a monovalent organic group
- i is an integer of 0 to 3
- j is an integer of 0 to 3
- ⁇ i + j ⁇ 5
- R 6 is a hydrogen atom or a methyl group
- R 7 is a hydrogen atom or a monovalent organic group
- k is an integer of 0 to 3
- l is an integer of 0 to 3
- R 8 is a hydrogen atom or a methyl group
- R 9 is a hydrogen atom or a monovalent organic group
- m is an integer of 0 to 3
- n is an integer of 0 to 3, and 0 ⁇ m + n ⁇ 5 .
- R 10 is a hydrogen atom or a methyl group
- R 11 is a hydrogen atom or a monovalent organic group
- r is an integer of 0 to 3
- R 5 is a hydrogen atom or a monovalent organic group, and when it is a monovalent organic group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, A linear or branched alkyl group having 1 to 12 carbon atoms such as 2-methylpropyl group, 1-methylpropyl group, tert-butyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group A linear or branched alkoxyl group having 1 to 12 carbon atoms such as n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, tert-butoxy group; cyclopentyl group, cyclohexyl group, cycloheptyl group Cycloalkyl groups such as cyclooctyl group, cyclodecanyl group, cyclododecanyl group; adamanty
- a methyl group, an ethyl group, an n-butyl group, and a tert-butyl group are preferable.
- i is an integer of 0 to 3, preferably 1 or 2.
- j is an integer of 0 to 3, preferably 0 to 2.
- repeating unit (2) represented by the general formula (2) examples include repeating units represented by the following formulas (2-1) to (2-4).
- this repeating unit (2) may be included alone or in combination of two or more.
- R 7 is a hydrogen atom or a monovalent organic group.
- the description regarding the monovalent organic group of R 5 in the general formula (2) is not changed. Can be applied.
- k is an integer of 0 to 3, preferably 1 or 2.
- l is an integer of 0 to 3, preferably 0 or 1.
- repeating unit (3) represented by the general formula (3) examples include repeating units represented by the following formulas (3-1) and (3-2).
- this repeating unit (3) may be included alone or in combination of two or more.
- R 9 is a hydrogen atom or a monovalent organic group, and when it is a monovalent organic group, the description regarding the monovalent organic group of R 5 in the general formula (2) is not changed. Can be applied.
- m is an integer of 0 to 3, preferably 1 or 2.
- n is an integer of 0 to 3, preferably 0 or 1.
- Examples of the repeating unit (4) represented by the general formula (4) include repeating units represented by the following formulas (4-1) and (4-2).
- this repeating unit (4) may be included alone or in combination of two or more.
- R 11 is a hydrogen atom or a monovalent organic group, when it is a monovalent organic group, as a description for the monovalent organic group for R 5 in formula (2) Can be applied.
- r is an integer of 0 to 3, preferably 1 or 2.
- s is an integer of 0 to 3, preferably 0 or 1.
- Examples of the repeating unit (5) represented by the general formula (5) include repeating units represented by the following formulas (5-1) and (5-2).
- repeating unit (N) represented by the general formula (N) examples include repeating units represented by the following formulas (N-1) and (N-2).
- this repeating unit (N) may be included in only one kind or in two kinds.
- the repeating units represented by the above formulas (2-1) to (2-3) can be formed by using the corresponding hydroxystyrene derivative as a monomer. Moreover, it can also form by using as a monomer the compound from which a hydroxystyrene derivative is obtained by hydrolysis before superposition
- the monomer used for forming the repeating units represented by the above formulas (2-1) to (2-3) p-acetoxystyrene, p- (1-ethoxyethoxy) styrene and the like are preferable.
- a repeating unit represented by the formulas (2-1) to (2-3) can be formed by a side chain hydrolysis reaction after forming a polymer. .
- the above formulas (2-4), (3-1), (3-2), (4-1), (4-2), (5-1), (5-2), (N-1 ) And (N-2) can be formed by using corresponding monomers.
- the above formulas (2-4), (3-1), (3-2), (4-1), (4-2), (5-1), (5-2), (N-1) and Examples of the monomer used to form the repeating unit represented by (N-2) include p-isopropenylphenol, 4-hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, 5-hydroxynaphthalen-1-yl methacrylate, 5-hydroxynaphthalen-1-yl acrylate, a compound represented by the following formula (n-1), a compound represented by the following formula (n-2 And the like are preferred.
- the polymer (I) of the present invention includes a repeating unit derived from a non-acid dissociable compound (hereinafter referred to as “repeating unit (6)”). And a repeating unit derived from an acid dissociable compound (hereinafter also referred to as “repeating unit (7)”).
- non-acid dissociable compound forming the repeating unit (6) examples include styrene, ⁇ -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, isobornyl acrylate, tricyclodecanyl (meta ) Acrylate, tetracyclododecenyl (meth) acrylate, and the like.
- styrene, ⁇ -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, and tricyclodecanyl acrylate are preferable.
- this repeating unit (6) may be included alone or in combination of two or more.
- Examples of the acid dissociable compound forming the repeating unit (7) include compounds represented by the following general formulas (7-1) and (7-2).
- R 12 independently represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group
- R 13 independently represents a straight-chain having 1 to 4 carbon atoms.
- a branched alkyl group a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a group derived therefrom, or any two R 13 's bonded to each other, A divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom with a carbon atom, and the remaining one R 13 is linear or branched having 1 to 4 carbon atoms Or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom.
- R 13 is a linear or branched alkyl group having 1 to 4 carbon atoms, a methyl group, an ethyl group, an n-propyl group
- examples include isopropyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, tert-butyl group and the like.
- R 13 is a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, etc. And groups composed of alicyclic rings derived from the cycloalkanes.
- examples of the group derived from the alicyclic hydrocarbon group include one or more hydrogen atoms bonded to carbon atoms constituting the monovalent alicyclic hydrocarbon group, for example, a methyl group, an ethyl group, and the like.
- a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms such as n-propyl group, isopropyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, tert-butyl group, etc. And the like, and the like.
- R 13 is a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, a group consisting of an alicyclic ring derived from norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane or cyclohexane
- a group in which at least one hydrogen atom bonded to a carbon atom constituting a group composed of these alicyclic rings is substituted with the alkyl group is preferable.
- any two R 13 out of the three R 13 are bonded to each other, and together with the carbon atom to which each R 13 is bonded (the carbon atom bonded to the oxygen atom), 2 having 4 to 20 carbon atoms.
- a valent alicyclic hydrocarbon group for example, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, and the like can be given.
- the group derived from a divalent alicyclic hydrocarbon group formed by bonding R 13 to each other includes a hydrogen atom bonded to the carbon atom constituting the divalent alicyclic hydrocarbon group.
- any two R 13 out of the three R 13 are bonded to each other, and together with the carbon atom to which each is bonded (the carbon atom bonded to the oxygen atom), the divalent divalent having 4 to 20 carbon atoms
- a divalent alicyclic hydrocarbon group such as a cyclopentylene group or a cyclohexylene group, and carbon atoms constituting the divalent alicyclic hydrocarbon group
- a group in which one or more hydrogen atoms bonded to is substituted with the alkyl group is preferable.
- repeating unit (7) examples include repeating units represented by the following general formulas (7-1a) to (7-1g) and (7-2a).
- R 12 is a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group
- R 13 is independently a linear or branched alkyl having 1 to 4 carbon atoms.
- a divalent alicyclic hydrocarbon group having 4 to 20 atoms or a group derived therefrom is formed, and the remaining one R 13 is a linear or branched alkyl group having 1 to 4 carbon atoms, Or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom.
- this repeating unit (7) may be included alone or in combination of two or more.
- the upper limit of the total content is the number of repetitions constituting the polymer (I).
- the total of the units is 100 mol%, it is preferably 99 mol%, more preferably 95 mol%, still more preferably 90 mol%.
- the polymer (I) of the present invention contains the above repeating unit (1), it is an alkali-insoluble or alkali-insoluble polymer that becomes readily alkali-soluble by the action of an acid. Therefore, it can be suitably used as an acid-dissociable group-containing polymer in the radiation-sensitive composition.
- the content of each repeating unit is as follows.
- the content of the repeating unit (1) is preferably 1 mol% or more, more preferably 5 to 70 mol%, still more preferably when the total number of repeating units constituting the polymer (I) is 100 mol%. Is 5 to 50 mol%. When this content is 1 mol% or more, a resist pattern excellent in nano edge roughness can be formed by the radiation-sensitive composition containing the polymer (I).
- the total content of the above repeating units (2) to (5) and (N) is preferably 1 mol% or more when the total of the repeating units constituting the polymer (I) is 100 mol%.
- the total content of the repeating units (1) to (5) and (N) is preferably 10 mol% or more when the total of the repeating units constituting the polymer (I) is 100 mol%. More preferably, it is 40 to 100 mol%, and still more preferably 50 to 100 mol%. When the total content is 10 mol% or more, a resist pattern excellent in nano edge roughness can be formed by the radiation-sensitive composition containing the polymer (I).
- the content of the repeating unit (6) is usually 80 mol% or less, preferably 0 to 60 mol% when the total of the repeating units constituting the polymer (I) is 100 mol%. It is. When the radiation-sensitive composition containing the polymer (I) having a content of 80 mol% or less is used, the performance balance between resolution performance and nanoedge roughness can be excellent. Further, the content of the repeating unit (7) is usually 60 mol% or less, preferably 0 to 50 mol%, when the total number of repeating units constituting the polymer (I) is 100 mol%. It is.
- the performance balance between resolution performance and nanoedge roughness can be excellent.
- the total content of the repeating units (6) and (7) is preferably 90 mol% or less, more preferably when the total of the repeating units constituting the polymer (I) is 100 mol%. 0 to 80 mol%.
- the performance balance between the resolution performance and the nano edge roughness can be particularly excellent.
- the production method of the polymer (I) of the present invention is not particularly limited, and a known radical polymerization or anion polymerization is performed using a monomer (mixture) containing a compound represented by the general formula (10). Can be obtained.
- a monomer (mixture) containing a compound represented by the general formula (10). Can be obtained.
- the polymer (I) having a hydroxystyrene unit in the side chain is used as in the above repeating units (2) to (5), the obtained precursor polymer is added to a base or a base in an organic solvent.
- Polymer (I) can be obtained by hydrolysis of an acetoxy group or the like in the presence of an acid.
- Radical polymerization may be, for example, a method in which the monomer (mixture) is heated with stirring in a nitrogen atmosphere in a suitable organic solvent in the presence of a radical polymerization initiator.
- radical polymerization initiator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2). , 4-Dimethylvaleronitrile) 2,2′-azobismethylbutyronitrile, 2,2′-azobiscyclohexanecarbonitrile, cyanomethylethylazoformamide, 2,2′-azobis (2,4-dimethylpropionic acid) Methyl), azo compounds such as 2,2′-azobiscyanovaleric acid; benzoyl peroxide, lauroyl peroxide, 1,1′-bis- (tert-butylperoxy) cyclohexane, 3,5,5-trimethylhexanoyl Organic peroxides such as peroxide and tert-butylperoxy-2-ethylhexanoate; hydrogen peroxide and the like.
- a polymerization a polymerization
- the reaction temperature in the radical polymerization is usually appropriately selected depending on the type of radical polymerization initiator (eg, 50 ° C. to 200 ° C.). In particular, when an azo compound or an organic peroxide is used, it is preferably a temperature at which the half-life is about 10 minutes to 30 hours, more preferably a temperature at which the half-life is about 30 minutes to 10 hours. .
- the reaction time varies depending on the type of initiator and the reaction temperature, but the reaction time during which 50% or more of the initiator is consumed is desirable, and in many cases, about 0.5 to 24 hours.
- Anionic polymerization can be, for example, a method in which the monomer (mixture) is maintained at a predetermined temperature while stirring in the presence of an anionic polymerization initiator in a suitable organic solvent in a nitrogen atmosphere. .
- anionic polymerization initiator examples include alkyllithium compounds such as n-butyllithium, s-butyllithium, tert-butyllithium, ethyllithium, 1,1-diphenylhexyllithium, and 1,1-diphenyl-3-methylpentyllithium.
- An organic alkali metal compound such as ethyl sodium;
- the reaction temperature in the anionic polymerization is usually appropriately selected depending on the type of anionic polymerization initiator and the like.
- the reaction temperature is preferably ⁇ 100 ° C. to 50 ° C., more preferably ⁇ 78 ° C. to 30 ° C.
- the reaction time varies depending on the type of initiator and the reaction temperature, but the reaction time during which 50% or more of the initiator is consumed is desirable, and in many cases, about 0.5 to 24 hours.
- the polymer (I) can be produced without using a polymerization initiator. For example, it is possible to perform a polymerization reaction by heating, and to perform cationic polymerization.
- acids used in this case include p-toluenesulfonic acid and hydrates thereof, methanesulfonic acid, trifluoromethanesulfonic acid, malonic acid, succinic acid, 1,1,1-fluoroacetic acid and other organic acids; sulfuric acid, hydrochloric acid And inorganic acids such as phosphoric acid and hydrobromic acid; salts of pyridinium p-toluenesulfonate, ammonium p-toluenesulfonate, 4-methylpyridinium p-toluenesulfonate, and the like.
- the base examples include inorganic bases such as potassium hydroxide, sodium hydroxide, sodium carbonate and potassium carbonate; organic bases such as triethylamine, N-methyl-2-pyrrolidone, piperidine and tetramethylammonium hydroxide.
- inorganic bases such as potassium hydroxide, sodium hydroxide, sodium carbonate and potassium carbonate
- organic bases such as triethylamine, N-methyl-2-pyrrolidone, piperidine and tetramethylammonium hydroxide.
- organic solvent used for the polymerization and the hydrolysis examples include ketones such as acetone, methyl ethyl ketone and methyl amyl ketone; ethers such as diethyl ether and tetrahydrofuran (THF); alcohols such as methanol, ethanol and propanol.
- ketones such as acetone, methyl ethyl ketone and methyl amyl ketone
- ethers such as diethyl ether and tetrahydrofuran (THF)
- alcohols such as methanol, ethanol and propanol.
- Aliphatic hydrocarbons such as hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; alkyl halides such as chloroform, bromoform, methylene chloride, methylene bromide and carbon tetrachloride; ethyl acetate , Esters such as butyl acetate, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cellosolves; non-prototypes such as dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide Sex polar solvent such like.
- acetone methyl amyl ketone, methyl ethyl ketone, tetrahydrofuran, methanol, ethanol, propanol, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable.
- the polymer (I) has a polystyrene-equivalent weight average molecular weight (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC), preferably 2000 to 100,000, more preferably 2000 to 40000, still more preferably. Is 2000-25000. Further, the ratio (Mw / Mn) of Mw of the polymer (I) and polystyrene-equivalent number average molecular weight (hereinafter also referred to as “Mn”) measured by GPC is usually 1 to 5, preferably 1 To 3, more preferably 1 to 2.5.
- Mw polystyrene-equivalent weight average molecular weight measured by GPC
- the radiation-sensitive composition of the present invention comprises an acid-dissociable group-containing polymer (A) and a radiation-sensitive acid generator (B), and an acid-dissociable group-containing polymer ( A) is the polymer (I).
- Acid-dissociable group-containing polymer (A) is the above-mentioned polymer (I), and is a polymer that is insoluble in alkali or hardly soluble in alkali and easily soluble in alkali by the action of an acid.
- the polymer (I) is a polymer (hereinafter referred to as “polymer”) containing the repeating unit (1) and at least one selected from the repeating units (2) to (7) and (N). (I-1) ”).
- alkali-insoluble or alkali-insoluble refers to the resist film under alkaline development conditions employed when a resist pattern is formed from the resist film formed from the radiation-sensitive composition of the present invention.
- a film having a film thickness of 100 nm is developed using only the polymer (I-1) instead of the above, it means that 50% or more of the initial film thickness of the film remains after the development.
- the radiation sensitive composition of the present invention contains the polymer (I-1), the sensitivity in the lithography process is excellent.
- the radiation-sensitive composition of the present invention in this lithography process, it is effective for (extreme) far ultraviolet rays such as KrF excimer laser, ArF excimer laser, EUV, X-rays such as synchrotron radiation, and electron beams. It is possible to form a chemically amplified positive resist film that is sensitive, has low roughness, is excellent in sensitivity and resolution, and can form a fine pattern with high accuracy and stability.
- Radiation sensitive acid generator (B) This radiation-sensitive acid generator (B) generates an acid in the film when the film obtained by using the radiation-sensitive composition of the present invention is irradiated with an electron beam or radiation in a lithography process. It is a substance.
- the acid-dissociable group in the polymer (I-1) is dissociated by the action of the acid generated from the radiation-sensitive acid generator (B).
- the radiation sensitive acid generator (B) is, for example, at least one selected from the group consisting of an onium salt, a diazomethane compound, and a sulfonimide compound from the viewpoint of good acid generation efficiency, heat resistance, and the like. It is preferable that In addition, these may be used individually by 1 type and may be used in combination of 2 or more type.
- the compound represented by the following general formula (b1) is preferable.
- M + Z ⁇ (b1) (Wherein M + is a monovalent onium cation and Z ⁇ is a monovalent anion.)
- onium salt examples include iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, pyridinium salt and the like. Of these, sulfonium salts and iodonium salts are preferred because of their excellent sensitivity.
- the monovalent onium cation represented by M + is preferably a sulfonium cation or an iodonium cation.
- Examples of the sulfonium cation include a cation represented by the following general formula (8-1).
- R 19 is independently of each other a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, or an aryl having 6 to 18 carbon atoms which may be substituted. Group, or any two R 19 s bonded to each other to form a cyclic structure together with the sulfur atom in the formula, and the remaining one R 19 is a straight chain having 1 to 10 carbon atoms which may be substituted.
- Examples of the iodonium cation include a cation represented by the following general formula (8-2).
- R 20 independently of each other is a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, or an aryl having 6 to 18 carbon atoms which may be substituted. group, or two R 20 are bonded to each other to form a cyclic structure together with the iodine atom in the formula.
- M + The monovalent onium cation moiety represented by M + is described in, for example, Advances in Polymer Sciences, Vol. 62, p. 1-48 (1984).
- examples of the monovalent onium anion represented by Z ⁇ include anions represented by the following general formulas (9-1), (9-2), (9-3) and (9-4). .
- R 20 SO 3 - (9-4) (In the general formula (9-1), R 14 and R 15 are each independently an alkyl group having 1 to 20 carbon atoms substituted with at least one fluorine atom, or R 14 and R 15 are They are bonded to each other to form a cyclic structure having 1 to 20 carbon atoms substituted with at least one fluorine atom, wherein in the general formula (9-2), R 16 , R 17 and R 18 are: Independently of each other, an alkyl group having 1 to 20 carbon atoms substituted with at least one fluorine atom, or any two of R 16 , R 17 and R 18 are bonded to each other to form at least one fluorine atom And the remaining one is an alkyl group having 1 to 20 carbon atoms substituted with at least one
- onium salt examples include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium benzenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium n-octanesulfonate, triphenylsulfonium 4 -Trifluoromethylbenzenesulfonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium perfluorobenzenesulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 2,5 .1,7,10 ] dodecan-8-yl) ethanesulfonate, triphenylsulfonium 1,1-difluor
- Examples thereof include compounds represented by the following formulas (2x-1) to (2x-42).
- These onium salts may be used alone or in combination of two or more.
- triphenylsulfonium trifluoromethanesulfonate triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium 10-camphorsulfonate, (4-hydroxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-hydroxy) Phenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, tris (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tris (4-methoxyphenyl) sulfonium nonafluoro-n-butanesulfonate, (4-fluorophenyl) diphenylsulfonium trifluoromethane Sulfonate, (4-fluorophenyl) diphenylsulfonium nonafluoro-n-butyl
- diazomethane compound examples include bis (trifluoromethanesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl) diazomethane, bis (1 , 4-dioxaspiro [4.5] decane-7-sulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, and the like. These diazomethane compounds may be used alone or in combination of two or more.
- diazomethane compounds bis (cyclohexylsulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl) diazomethane and bis (1,4-dioxaspiro [4. 5] Decane-7-sulfonyl) diazomethane is preferred.
- sulfonimide compound examples include N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7- Oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2, 3-dicarboximide; N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [ 2.1] heptane-5,6-oxy-2,3-dica
- N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) succinimide and N-[(5-methyl-5-carboxymethylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] succinimide is preferred.
- the content of the radiation-sensitive acid generator (B) in the radiation-sensitive composition of the present invention is preferably 0.1 to 50 masses with respect to 100 mass parts of the acid-dissociable group-containing polymer (A). Part, more preferably 0.5 to 50 parts by weight. There exists a possibility that a sensitivity and developability may fall that content of this acid generator (B) is less than 0.1 mass part. On the other hand, when the content exceeds 50 parts by mass, the transparency to radiation, pattern shape, heat resistance, and the like may be reduced.
- the radiation sensitive composition of the present invention comprises an acid diffusion control agent (hereinafter referred to as “acid diffusion control agent”). (C) ”) is preferably further contained.
- the acid diffusion controller (C) is a diffusion phenomenon of an acid generated from the radiation-sensitive acid generator (B) in the resist film (resist film) by exposure of the film obtained by using the composition of the present invention. Is a component having an action of controlling undesired chemical reactions in non-exposed areas.
- the storage stability of the resulting radiation-sensitive composition is improved and the resolution of the resist film to be formed is reduced. It can be improved sufficiently. Furthermore, it is possible to suppress changes in the line width of the resist pattern due to fluctuations in the holding time (PED) from the exposure to the heat treatment after the exposure, thereby obtaining a radiation-sensitive composition having extremely excellent process stability. It is done.
- Examples of the acid diffusion controller (C) include nitrogen-containing organic compounds and photosensitive basic compounds. These may be used individually by 1 type and may be used in combination of 2 or more type.
- Examples of the nitrogen-containing organic compound include a compound represented by the following general formula (12) (hereinafter referred to as “nitrogen-containing compound (i)”), a compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound”).
- nitrogen-containing compound (i) a compound represented by the following general formula (12)
- nitrogen-containing compound (i) a compound represented by the following general formula (12)
- nitrogen-containing compound (i) a compound represented by the following general formula (12)
- nitrogen-containing compound (i) a compound represented by the following general formula (12)
- nitrogen-containing compound (i) a compound represented by the following general formula (12)
- nitrogen-containing compound (i) a compound represented by the following general formula (12)
- nitrogen-containing compound (i) a compound having two nitrogen atoms in the same molecule
- R 21 s are independently of each other a hydrogen atom, a linear, branched or cyclic optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl. Group.
- nitrogen-containing compound (i) examples include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine; di-n-butylamine Di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine, etc.
- mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine; di-n-butylamine Di-n-pentylamine, di
- (Cyclo) alkylamines triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, Tri-n-nonylamine, tri-n-decylamine, cyclohexyl Tri (cyclo) alkylamines such as methylamine, methyldicyclohexylamine, and tricyclohexylamine; substituted alkylamines such as triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3- Methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2,4,6-tri-tert-butyl-N-methylaniline, N-phenyldiethanolamine, 2,6-diisopropylani
- nitrogen-containing compound (ii) examples 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-aminophenyl) -1-methylethyl]
- the nitrogen-containing compound (iii) is preferably a polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide polymer, or the like. These may be used alone or in combination of two or more.
- Examples of the amide group-containing compound include N-tert-butoxycarbonyldi-n-octylamine, N-tert-butoxycarbonyldi-n-nonylamine, N-tert-butoxycarbonyldi-n-decylamine, N-tert-butoxy.
- urea compound examples include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea, etc. Is mentioned. These may be used alone or in combination of two or more.
- nitrogen-containing heterocyclic compound examples include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-methyl.
- Imidazoles such as -1H-imidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, Pyridines such as nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, 2,2 ′: 6 ′, 2 ′′ -terpyridine; piperazine, 1- (2-hydroxyethyl )
- piperazines such as piperazine, Gin, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, piperidine ethanol, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, 3 -(N-morpholino) -1,
- the photosensitive basic compound is a component that decomposes in the exposed region and loses basicity, and remains in the unexposed portion without being decomposed. Since such a photosensitive basic compound can effectively use an acid generated in an exposed portion (that is, an exposed region), compared with a non-photosensitive basic compound, sensitivity can be further improved. .
- Examples of the photosensitive basic compound include compounds represented by the following general formulas (14-1) and (14-2).
- R 23 may independently have a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent.
- R 24 each independently represents a hydrogen atom, a halogen atom, or an aryl group that may have a substituent.
- a cycloaliphatic hydrocarbon group or a substituted group is also an aryl group .Z 2 - may, OH -, R 27 O -, or R 27 COO - and is, R 27 is a monovalent organic radical .
- R 23 and R 24 are preferably a hydrogen atom and a tert-butyl group.
- all of the plurality of R 23 may be the same or a part or all of them may be different.
- two R 24 may be the same or different.
- R 27 is a monovalent organic group.
- the monovalent organic group represented by R 27, the substituent alkyl group which may have a substituted aryl group and the like may have a substituent.
- Z 2 - The, OH -, CH 3 COO - , and ions (15-1) of the following formula - (15-5) are preferable.
- the photosensitive basic compound is a triphenylsulfonium compound represented by the above general formula (14-1), and its anion portion (Z 2 ⁇ ) is OH ⁇ , CH 3 COO ⁇ , -2) or (15-3).
- the content of the acid diffusion controller (C) in the radiation-sensitive composition of the present invention is preferably 30 parts by mass or less, more preferably 100 parts by mass with respect to 100 parts by mass of the acid dissociable group-containing polymer (A).
- the amount is 0.001 to 30 parts by mass, more preferably 0.005 to 15 parts by mass.
- the radiation-sensitive composition of the present invention is obtained by dissolving the acid dissociable group-containing polymer (A), the radiation-sensitive acid generator (B), and the acid diffusion controller (C) in a solvent. It is preferable that That is, it is preferable to contain a solvent as other components. Moreover, additives, such as surfactant, a sensitizer, an aliphatic additive, can be mix
- Examples of the solvent include linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, alkyl 2-hydroxypropionate, alkyl 3-alkoxypropionate, and ⁇ -butyrolactone. It is done. These may be used alone or in combination of two or more.
- the content of the solvent in the radiation-sensitive composition of the present invention is such that the total solid concentration in the composition is preferably 1 to 70% by mass, more preferably 1 to 15% by mass, and still more preferably 1 to 10% by mass. % Is set.
- the surfactant is a component having an effect of improving coatability, striation, developability and the like.
- Such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene
- nonionic surfactants such as glycol distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no.
- the content thereof is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass of the acid-dissociable group-containing polymer (A). It is.
- the sensitizer absorbs radiation energy and transmits the energy to the radiation-sensitive acid generator (B), thereby increasing the amount of acid produced.
- the radiation-sensitive composition It has the effect of improving the apparent sensitivity.
- Examples of such sensitizers include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines, and the like. These sensitizers may be used individually by 1 type, and may be used in combination of 2 or more type.
- the content thereof is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the acid-dissociable group-containing polymer (A). It is.
- the said alicyclic additive is a component which has the effect
- Such alicyclic additives include 1-adamantanecarboxylic acid, 2-adamantanone, tert-butyl 1-adamantanecarboxylate, tert-butoxycarbonylmethyl 1-adamantanecarboxylate, ⁇ -butyrolactone 1-adamantanecarboxylic acid Esters, 1,3-adamantane dicarboxylate di-tert-butyl, 1-adamantane acetate tert-butyl, 1-adamantane acetate tert-butoxycarbonylmethyl, 1,3-adamantane diacetate di-tert-butyl, 2,5- Adamantane derivatives such as dimethyl-2,5-di (adamantylcarbonyloxy) hexane; tert-buty
- the content thereof is preferably 0.5 to 20 with respect to 100 parts by mass of the acid-dissociable group-containing polymer (A). Part by mass.
- the heat resistance of the formed resist film may fall.
- additives other than the above include alkali-soluble polymers, low-molecular alkali-solubility control agents having acid-dissociable protecting groups, antihalation agents, storage stabilizers, antifoaming agents, and the like. Further, by blending a dye or pigment, the latent image in the exposed area can be visualized, and the influence of halation during exposure can be reduced. Furthermore, the adhesiveness of a resist film and a board
- the radiation-sensitive composition of the present invention comprises a polymer (A), a radiation-sensitive acid generator (B), an acid diffusion controller (C), and, if necessary, other components (excluding the solvent) It can be prepared by uniformly dissolving in a solvent so that the concentration is in the above range. In addition, after preparing in this way, it is preferable to filter with a filter with a pore diameter of about 0.2 ⁇ m, for example.
- the radiation-sensitive composition of the present invention is useful as a material capable of forming a chemically amplified positive resist film.
- the acid-dissociable group in the polymer is eliminated by the action of the acid generated from the radiation-sensitive acid generator by exposure, and the polymer becomes alkali-soluble. That is, an alkali-soluble site is generated in the resist film.
- This alkali-soluble portion is an exposed portion of the resist, and this exposed portion can be dissolved and removed by an alkali developer. In this way, a positive resist pattern having a desired shape can be formed. This will be specifically described below.
- a resist film is formed using the radiation-sensitive composition of the present invention.
- the radiation-sensitive composition for example, as described above, after adjusting the total solid content concentration, a composition filtered with a filter having a pore diameter of about 0.2 ⁇ m can be used.
- a resist film is formed by applying this radiation-sensitive composition onto a substrate such as a silicon wafer or a wafer coated with aluminum by an appropriate application means such as spin coating, cast coating or roll coating. Thereafter, if necessary, heat treatment (hereinafter referred to as “PB”) may be performed at a temperature of about 70 ° C. to 160 ° C. in advance.
- PB heat treatment
- the coating film is irradiated with radiation illustrated below through a photomask having a mask pattern for forming a desired pattern so that a predetermined resist pattern is formed, that is, exposed.
- radiation that can be used for this exposure include (extreme) far ultraviolet rays such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), EUV (extreme ultraviolet light, wavelength 13.5 nm, etc.), and synchrotron radiation.
- charged particle beams such as X-rays and electron beams.
- exposure conditions, such as exposure amount can be suitably selected according to the compounding composition of a radiation sensitive composition, the kind of additive, etc. This exposure can also be immersion exposure.
- PEB heat processing
- the radiation-sensitive composition in order to maximize the potential of the radiation-sensitive composition, it is used, for example, as disclosed in Japanese Patent Publication No. 6-12452 (Japanese Patent Laid-Open No. 59-93448).
- An organic or inorganic antireflection film can also be formed on the substrate.
- a protective film can be provided on the resist film as disclosed in, for example, Japanese Patent Laid-Open No. 5-188598. These techniques can be used in combination.
- a predetermined resist pattern is formed by developing the exposed resist film.
- an alkaline aqueous solution obtained by dissolving an alkaline compound in water is usually used.
- the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethyl Dimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene and the like. These may be used alone or in combination of two or more.
- the concentration of the alkaline compound is preferably 10% by mass or less. When the concentration of the alkaline compound exceeds 10% by mass, the unexposed area may be dissolved in the developer.
- the pH of the developer is preferably pH 8 to pH 14, more preferably pH 9 to pH 14.
- the developer may be a solution containing only the alkaline compound or a composition containing an organic solvent, a surfactant, and the like.
- organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetonyl acetone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethylcyclohexanone; methyl alcohol, ethyl alcohol, n- Alcohols such as propyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane; Examples include esters such as ethyl acetate, n-butyl acetate and isoa
- the said organic solvent may be used independently and may be used in combination of 2 or more.
- the content thereof is preferably 100 parts by volume or less with respect to 100 parts by volume of the alkaline aqueous solution. If the content of the organic solvent exceeds 100 parts by volume, the developability is lowered, and there is a possibility that the development residue in the exposed part increases. After developing with the developer, washing and drying are usually performed.
- Mw and Mn were determined using monodisperse polystyrene as a standard. Further, the degree of dispersion Mw / Mn was calculated from both data.
- 13 C-NMR analysis The measurement was carried out using a nuclear magnetic resonance apparatus “JNM-EX270” (model name) manufactured by JEOL Ltd.
- this copolymer As a result of 13 C-NMR analysis, it was a copolymer with a content ratio (molar ratio) of each repeating unit derived from p-hydroxystyrene and the compound (X-1-1) of 66:34. Hereinafter, this copolymer is referred to as a polymer (A-1).
- Polymer Production Example 3 [Synthesis of Polymer (A-3)] Copolymerization was conducted in the same manner as in Polymer Production Example 1 except that Compound (X-1-2) obtained in Monomer Synthesis Example 2 was used instead of Compound (X-1-1). A coalescence was produced.
- the obtained copolymer had Mw of 12000 and Mw / Mn of 2.5.
- As a result of 13 C-NMR analysis it was a copolymer having a content ratio (molar ratio) of each repeating unit derived from p-hydroxystyrene and the compound (X-1-2) of 67:33.
- this copolymer is referred to as a polymer (A-3).
- Polymer Production Example 4 [Synthesis of Polymer (A-4)] Copolymerization was performed in the same manner as in Polymer Production Example 1 except that Compound (X-1-3) obtained in Monomer Synthesis Example 3 was used instead of Compound (X-1-1). A coalescence was produced.
- the obtained copolymer had Mw of 11000 and Mw / Mn of 2.6.
- As a result of 13 C-NMR analysis it was a copolymer with a content ratio (molar ratio) of each repeating unit derived from p-hydroxystyrene and the compound (X-1-3) of 65:35.
- this copolymer is referred to as a polymer (A-4).
- Polymer Production Example 6 [Synthesis of Polymer (A-6)] Copolymerization was carried out in the same manner as in Polymer Production Example 1 except that compound (X-1-5) obtained in monomer synthesis example 5 was used instead of compound (X-1-1). A coalescence was produced.
- the obtained copolymer had Mw of 11000 and Mw / Mn of 2.4.
- As a result of 13 C-NMR analysis it was a copolymer with a content ratio (molar ratio) of each repeating unit derived from p-hydroxystyrene and the compound (X-1-5) of 68:32.
- this copolymer is referred to as “polymer (A-6)”.
- a resist pattern was formed and evaluated in the following manner. These results are shown in Table 2.
- a radiation sensitive composition was spin-coated on a silicon wafer, and then PB (heat treatment) was performed under the conditions shown in Table 2 to form a resist film having a film thickness of 60 nm. Formed. Thereafter, the resist film was irradiated with an electron beam using a simple electron beam drawing apparatus (manufactured by Hitachi, Ltd., model “HL800D”, output: 50 KeV, current density: 5.0 amperes / cm 2 ). After the electron beam irradiation, PEB was performed under the conditions shown in Table 2.
- Sensitivity (L / S) A pattern (a so-called line-and-space pattern (1L1S)) composed of a line portion having a line width of 150 nm and a space portion (that is, a groove) having an interval of 150 nm formed by adjacent line portions is 1: 1.
- the exposure amount formed in the line width was set as the optimum exposure amount, and the sensitivity was evaluated based on the optimum exposure amount.
- FIG. 1 is a plan view schematically showing the shape of a line and space pattern.
- FIG. 2 is a cross-sectional view schematically showing the shape of the line and space pattern. However, the unevenness shown in FIGS. 1 and 2 is exaggerated from the actual.
- Nano-edge roughness Line-and-space pattern (1L1S) with a design line width of 150 nm is scanned with a scanning electron microscope for semiconductors (high resolution FEB measuring device, trade name “S-9220”, manufactured by Hitachi, Ltd.) ).
- high resolution FEB measuring device trade name “S-9220”, manufactured by Hitachi, Ltd.
- FIG. 1 and FIG. 2 the line width and the design line at the most conspicuous portion of the unevenness generated along the lateral surface 2a of the line portion 2 of the resist film formed on the silicon wafer 1 are shown.
- the difference “ ⁇ CD” from the width of 150 nm was measured by CD-SEM (manufactured by Hitachi High-Technologies Corporation, “S-9220”) to evaluate nanoedge roughness.
- the radiation-sensitive compositions of Examples 1 to 15 containing the polymers (A-1) to (A-6) are Comparative Examples 1 and 2 containing the polymer (A-7). Compared to other radiation-sensitive compositions, it is more sensitive to electron beams or extreme ultraviolet rays, has low roughness and excellent sensitivity and resolution, and can form fine patterns with high accuracy and stability. It was confirmed that a positive chemically amplified positive resist film could be formed.
- the radiation-sensitive composition of the present invention is not only excellent in the resolution of the line and space pattern at the time of pattern formation, but also excellent in nano edge roughness, and thus is useful for fine pattern formation by EB, EUV or X-ray. . Therefore, the radiation-sensitive composition of the present invention is extremely useful as a material capable of forming a chemically amplified resist for manufacturing semiconductor devices, which is expected to be further miniaturized in the future.
Abstract
Description
KrFエキシマレーザー光、電子線、或いはEUV光を用いたリソグラフィープロセスに適したレジストとしては、高感度化の観点から主に酸触媒反応を利用した化学増幅型レジストが用いられており、ポジ型レジストにおいては主成分として、アルカリ水溶液には不溶又は難溶性で、酸の作用によりアルカリ水溶液に可溶となる性質を有するフェノール性ポリマー(以下、「フェノール性酸分解性重合体」という)、及び酸発生剤からなる化学増幅型レジスト組成物が有効に使用されている。
1.下記一般式(1)で表される繰り返し単位を含むことを特徴とする重合体。
R2は置換若しくは非置換の炭素原子数6~22のアリール基であり、
Yは炭素原子であり、
XはYとともにヘテロ原子を含む環状構造を形成するのに必要な原子団であって、-X1Z1X2-を表し、Z1は-O-、-S-、-CO-、-COO-、-SO-若しくは-SO2-であり、X1及びX2は、互いに同一又は異なって、単結合、メチレン基又は炭素原子数2~25のアルキレン基であり、X1及びX2は置換基を有してもよく、X1及びX2はそれぞれに存在する炭素原子どうしが2価の基で結合されてもよい。)
2.上記一般式(1)で表される繰り返し単位が、下記一般式(1-1)で表される繰り返し単位である上記1に記載の重合体。
R1は水素原子、メチル基、フッ素原子又はトリフルオロメチル基であり、
R3は1価の有機基、ヒドロキシル基又はハロゲン原子であり、
Yは炭素原子であり、
XはYとともにヘテロ原子を含む環状構造を形成するのに必要な原子団であって、-X1Z1X2-を表し、Z1は-O-、-S-、-CO-、-COO-、-SO-若しくは-SO2-であり、X1及びX2は、互いに同一又は異なって、単結合、メチレン基又は炭素原子数2~25のアルキレン基であり、X1及びX2は置換基を有してもよく、X1及びX2はそれぞれに存在する炭素原子どうしが2価の基で結合されてもよい。)
3.更に、下記一般式(2)で表される繰り返し単位、下記一般式(3)で表される繰り返し単位、下記一般式(4)で表される繰り返し単位、下記一般式(5)で表される繰り返し単位、及び、下記一般式(N)で表される繰り返し単位から選ばれた少なくとも1種を含む上記1又は2に記載の重合体。
4.酸解離性基含有重合体(A)と、感放射線性酸発生剤(B)と、を含有する感放射線性組成物であって、
上記酸解離性基含有重合体(A)が、上記1乃至3のいずれかに記載の重合体であることを特徴とする感放射線性組成物。
5.上記感放射線性酸発生剤(B)が、下記一般式(b1)で表される化合物である上記4に記載の感放射線性組成物。
M+Z- (b1)
(式中、M+は1価のオニウムカチオンであり、Z-は下記一般式(9-1)又は(9-2)で表される1価のアニオンである。)
6.下記一般式(10)で表される化合物であることを特徴とする単量体。
R2は置換若しくは非置換の炭素原子数6~22のアリール基であり、
Yは炭素原子であり、
XはYとともにヘテロ原子を含む環状構造を形成するのに必要な原子団であって、-X1Z1X2-を表し、Z1は-O-、-S-、-CO-、-COO-、-SO-若しくは-SO2-であり、X1及びX2は、互いに同一又は異なって、単結合、メチレン基又は炭素原子数2~25のアルキレン基であり、X1及びX2は置換基を有してもよく、X1及びX2はそれぞれに存在する炭素原子どうしが2価の基で結合されてもよい。)
7.下記一般式(10)で表される化合物の製造方法。
R2は置換若しくは非置換の炭素原子数6~22のアリール基であり、
Yは炭素原子であり、
XはYとともにヘテロ原子を含む環状構造を形成するのに必要な原子団であって、-X1Z1X2-を表し、Z1は-O-、-S-、-CO-、-COO-、-SO-若しくは-SO2-であり、X1及びX2は、互いに同一又は異なって、単結合、メチレン基又は炭素原子数2~25のアルキレン基であり、X1及びX2は置換基を有してもよく、X1及びX2はそれぞれに存在する炭素原子どうしが2価の基で結合されてもよい。)
本発明の感放射線性組成物によれば、KrFエキシマレーザー、ArFエキシマレーザー、EUV等の(極)遠紫外線、シンクロトロン放射線等のX線、電子線に有効に感応し、ナノエッジラフネス、感度及び解像度に優れ、微細パターンを高精度に且つ安定して形成可能な化学増幅型ポジ型レジスト膜を形成することができる。
また、本発明の単量体は、上記本発明の重合体を好適に形成することができる。
1.重合体
本発明の重合体(以下、「重合体(I)」という)は、下記一般式(1)で表される繰り返し単位(以下、「繰り返し単位(1)」という)を含むことを特徴とする。
下記の(x-1)~(x-3)は、非置換の構造を示したものであるが、置換基を有する構造であってもよい。この置換基としては、メチル基、エチル基、プロピル基、ヒドロキシル基、カルボキシル基、ハロゲン原子(フッ素原子、塩素原子、臭素原子等)、アルコキシ基(メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等)、アルキルオキシカルボニル基等が挙げられる。
上記一般式(1-1)において、nは0~3の整数であり、好ましくは0~1である。
上記一般式(1-1)において、nが2又は3である場合、複数のR3は、互いに同一であってよいし、異なってもよい。
R2は置換若しくは非置換の炭素原子数6~22のアリール基であり、
Yは炭素原子であり、
XはYとともにヘテロ原子を含む環状構造を形成するのに必要な原子団であって、-X1Z1X2-を表し、Z1は-O-、-S-、-CO-、-COO-、-SO-若しくは-SO2-であり、X1及びX2は、互いに同一又は異なって、単結合、メチレン基又は炭素原子数2~25のアルキレン基であり、X1及びX2は置換基を有してもよく、X1及びX2はそれぞれに存在する炭素原子どうしが2価の基で結合されてもよい。)
以下は、上記一般式(1-1-1)で表した繰り返し単位を形成可能な化合物(1-1-1a)の製造例であり、この化合物(1-1-1a)は、下記一般式(1-r1)で表される化合物と、下記一般式(1-r2)で表される化合物との反応により製造することができる。
尚、本発明の重合体(I)における上記繰り返し単位(1)の含有量の下限は、重合体(I)を構成する繰り返し単位の合計を100モル%とした場合に、好ましくは1モル%、より好ましくは5モル%、更に好ましくは10モル%である。
上記一般式(2)におけるiは0~3の整数であり、好ましくは1又は2である。
また、上記一般式(2)におけるjは0~3の整数であり、好ましくは0~2である。
上記一般式(3)におけるkは0~3の整数であり、好ましくは1又は2である。
また、上記一般式(3)におけるlは0~3の整数であり、好ましくは0又は1である。
上記一般式(4)におけるmは0~3の整数であり、好ましくは1又は2である。
また、上記一般式(4)におけるnは0~3の整数であり、好ましくは0又は1である。
上記一般式(5)におけるrは0~3の整数であり、好ましくは1又は2である。
また、上記一般式(5)におけるsは0~3の整数であり、好ましくは0又は1である。
上記式(2-1)~(2-3)で表される繰り返し単位の形成に用いられる単量体としては、p-アセトキシスチレン、p-(1-エトキシエトキシ)スチレン等が好ましい。これらの単量体を用いた場合には、重合体とした後、側鎖の加水分解反応により、式(2-1)~(2-3)で表される繰り返し単位を形成することができる。
上記式(2-4)、(3-1)、(3-2)、(4-1)、(4-2)、(5-1)、(5-2)、(N-1)及び(N-2)で表される繰り返し単位の形成に用いられる単量体としては、p-イソプロペニルフェノール、4-ヒドロキシフェニルアクリレート、4-ヒドロキシフェニルメタクリレート、N-(4-ヒドロキシフェニル)アクリルアミド、N-(4-ヒドロキシフェニル)メタクリルアミド、5-ヒドロキシナフタレン-1-イルメタクリレート、5-ヒドロキシナフタレン-1-イルアクリレート、下記式(n-1)で表される化合物、下記式(n-2)で表される化合物等が好ましい。
また、この脂環式炭化水素基から誘導される基としては、上記1価の脂環式炭化水素基を構成する炭素原子に結合した水素原子の1つ以上が、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、2-メチルプロピル基、1-メチルプロピル基、tert-ブチル基等の炭素原子数1~4の直鎖状、分岐状又は環状のアルキル基に置換されてなる基等が挙げられる。
R13が、炭素原子数4~20の1価の脂環式炭化水素基である場合、ノルボルナン、トリシクロデカン、テトラシクロドデカン、アダマンタン、シクロペンタン又はシクロヘキサンに由来する脂環族環からなる基や、これらの脂環族環からなる基を構成する炭素原子に結合した水素原子の1つ以上が、上記アルキル基に置換されてなる基等が好ましい。
更に、R13が相互に結合して形成された2価の脂環式炭化水素基から誘導される基としては、上記2価の脂環式炭化水素基を構成する炭素原子に結合した水素原子の1つ以上が、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、2-メチルプロピル基、1-メチルプロピル基、tert-ブチル基等の炭素原子数1~4の直鎖状、分岐状又は環状のアルキル基に置換されてなる基等が挙げられる。
3つのR13のうちのいずれか2つのR13が相互に結合して、それぞれが結合している炭素原子(酸素原子に結合している炭素原子)とともに炭素原子数4~20の2価の脂環式炭化水素基を形成している場合、シクロペンチレン基、シクロヘキシレン基等の2価の脂環式炭化水素基、並びに、この2価の脂環式炭化水素基を構成する炭素原子に結合した水素原子の1つ以上が、上記アルキル基に置換されてなる基等が好ましい。
上記繰り返し単位(1)の含有量は、重合体(I)を構成する繰り返し単位の合計を100モル%としたときに、好ましくは1モル%以上、より好ましくは5~70モル%、更に好ましくは5~50モル%である。この含有量が1モル%以上である場合には、重合体(I)を含む感放射線性組成物により、ナノエッジラフネスに優れたレジストパターンを形成することができる。
また、上記繰り返し単位(2)~(5)及び(N)の含有量の合計は、重合体(I)を構成する繰り返し単位の合計を100モル%としたときに、好ましくは1モル%以上、より好ましくは5~95モル%、更に好ましくは5~95モル%である。この含有量の合計が95モル%を超える場合には、重合体(I)を含む感放射線性組成物により、十分なナノエッジラフネスを有するレジストパターンが形成されない場合がある。
更に、上記繰り返し単位(1)~(5)及び(N)の含有量の合計は、重合体(I)を構成する繰り返し単位の合計を100モル%としたときに、好ましくは10モル%以上、より好ましくは40~100モル%、更に好ましくは50~100モル%である。この含有量の合計が10モル%以上である場合には、重合体(I)を含む感放射線性組成物により、ナノエッジラフネスに優れたレジストパターンを形成することができる。
更に、上記繰り返し単位(7)の含有量は、重合体(I)を構成する繰り返し単位の合計を100モル%としたときに、通常、60モル%以下であり、好ましくは0~50モル%である。この含有量が60モル%以下である重合体(I)を含む感放射線性組成物を用いると、解像性能とナノエッジラフネスとの性能バランスに優れるものとすることができる。
また、上記繰り返し単位(6)及び(7)の含有量の合計は、重合体(I)を構成する繰り返し単位の合計を100モル%としたときに、好ましくは90モル%以下、より好ましくは0~80モル%である。この含有量が90モル%以下である重合体(I)を含む感放射線性組成物を用いると、解像性能とナノエッジラフネスとの性能バランスに特に優れるものとすることができる。
尚、このラジカル重合の際には、必要に応じて、2,2,6,6-テトラメチル-1-ピペリジニルオキシ、沃素、メルカプタン、スチレンダイマー等の重合助剤を添加することもできる。
また、反応時間は、開始剤の種類や反応温度により異なるが、開始剤が50%以上消費される反応時間が望ましく、多くの場合、0.5~24時間程度である。
また、反応時間は、開始剤の種類や反応温度により異なるが、開始剤が50%以上消費される反応時間が望ましく、多くの場合、0.5~24時間程度である。
また、塩基としては、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム等の無機塩基;トリエチルアミン、N-メチル-2-ピロリドン、ピペリジン、テトラメチルアンモニウムヒドロキシド等の有機塩基等が挙げられる。
これらのうち、アセトン、メチルアミルケトン、メチルエチルケトン、テトラヒドロフラン、メタノール、エタノール、プロパノール、酢酸エチル、酢酸ブチル、乳酸エチル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等が好ましい。
また、重合体(I)のMwと、GPCで測定したポリスチレン換算数平均分子量(以下、「Mn」ともいう)との比(Mw/Mn)は、通常、1~5であり、好ましくは1~3、より好ましくは1~2.5である。
本発明の感放射線性組成物は、酸解離性基含有重合体(A)と、感放射線性酸発生剤(B)と、を含有し、酸解離性基含有重合体(A)が上記重合体(I)であることを特徴とする。
この酸解離性基含有重合体(A)は、上記重合体(I)であり、アルカリ不溶性又はアルカリ難溶性であり且つ酸の作用によりアルカリ易溶性となる重合体である。そして、この重合体(I)は、上記繰り返し単位(1)と、上記繰り返し単位(2)~(7)及び(N)から選ばれた少なくとも1種とを含む重合体(以下、「重合体(I-1)」という)であることが好ましい。尚、ここでいう「アルカリ不溶性又はアルカリ難溶性」とは、本発明の感放射線性組成物から形成されたレジスト被膜からレジストパターンを形成する際に採用されるアルカリ現像条件下で、当該レジスト被膜の代わりに、重合体(I-1)のみを用いて膜厚100nmの被膜を現像した場合に、当該被膜の初期膜厚の50%以上が現像後に残存する性質を意味する。
この感放射線性酸発生剤(B)は、リソグラフィープロセスにおいて、本発明の感放射線性組成物を用いて得られた被膜に電子線や放射線等を照射したときに、該被膜内で酸を発生する物質である。そして、感放射線性酸発生剤(B)から発生した酸の作用によって、上記重合体(I-1)中の酸解離性基が解離することになる。
M+Z- (b1)
(式中、M+は1価のオニウムカチオンであり、Z-は1価のアニオンである。)
R20SO3 - (9-4)
(上記一般式(9-1)において、R14及びR15は、相互に独立に、少なくとも1つのフッ素原子で置換された炭素原子数1~20のアルキル基、或いは、R14及びR15が相互に結合して、少なくとも1つのフッ素原子で置換された炭素原子数1~20の環状構造を形成している。上記一般式(9-2)において、R16、R17及びR18は、相互に独立に、少なくとも1つのフッ素原子で置換された炭素原子数1~20のアルキル基、或いは、R16、R17及びR18のいずれか2つが相互に結合して、少なくとも1つのフッ素原子で置換された炭素原子数1~20の環状構造を形成しており、残りの1つが、少なくとも1つのフッ素原子で置換された炭素原子数1~20のアルキル基である。上記一般式(9-3)において、R19は、フッ素原子又は置換されていてもよい炭素原子数1~12の炭化水素基であり、nは1~10の整数である。上記一般式(9-4)において、R20は、フッ素原子又は置換されていてもよい炭素原子数1~12の炭化水素基である。)
これらのジアゾメタン化合物は、単独で用いてよいし、2つ以上を組み合わせて用いてもよい。
これらのジアゾメタン化合物のうち、ビス(シクロヘキシルスルホニル)ジアゾメタン、ビス(3,3-ジメチル-1,5-ジオキサスピロ[5.5]ドデカン-8-スルホニル)ジアゾメタン及びビス(1,4-ジオキサスピロ[4.5]デカン-7-スルホニル)ジアゾメタンが好ましい。
これらのスルホンイミド化合物は、単独で用いてよいし、2つ以上を組み合わせて用いてもよい。
本発明の感放射線性組成物は、上記酸解離性基含有重合体(A)及び感放射線性酸発生剤(B)以外に、酸拡散制御剤(以下、「酸拡散制御剤(C)」という)を更に含有することが好ましい。
酸拡散制御剤(C)は、本発明の組成物を用いて得られた被膜への露光により、感放射線性酸発生剤(B)から生じる酸の、レジスト膜(レジスト被膜)中における拡散現象を制御し、非露光領域における好ましくない化学反応を抑制する作用を有する成分である。
本発明の感放射線性組成物においては、この酸拡散制御剤(C)が配合されることにより、得られる感放射線性組成物の貯蔵安定性が向上すると共に、形成されるレジスト膜の解像度を十分に向上させることができる。更には、露光後から露光後の加熱処理までの引き置き時間(PED)の変動に起因するレジストパターンの線幅変化を抑えることができ、プロセス安定性に極めて優れた感放射線性組成物が得られる。
上記含窒素有機化合物としては、下記一般式(12)で表される化合物(以下、「含窒素化合物(i)」という)、同一分子内に窒素原子を2個有する化合物(以下、「含窒素化合物(ii)」という)、窒素原子を3個以上有するポリアミノ化合物や重合体(以下、これらをまとめて「含窒素化合物(iii)」という)、アミド基含有化合物、ウレア化合物、含窒素複素環化合物等が挙げられる。これらは、1種単独で用いてよいし、2種以上を組み合わせて用いてもよい。
R27を示す1価の有機基としては、置換基を有してもよいアルキル基、置換基を有してもよいアリール基等が挙げられる。
Z2 -としては、OH-、CH3COO-、及び、下記式で表されるイオン(15-1)~(15-5)が好ましい。
本発明の感放射線性組成物は、上記酸解離性基含有重合体(A)、感放射線性酸発生剤(B)及び酸拡散制御剤(C)を、溶剤に溶解させたものであることが好ましい。即ち、その他の成分として、溶剤を含有することが好ましい。
また、本発明の感放射線性組成物には、必要に応じて、界面活性剤、増感剤、脂肪族添加剤等の添加剤が配合されてなるものとすることができる。
このような界面活性剤としては、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンn-オクチルフェニルエーテル、ポリオキシエチレンn-ノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート等のノニオン系界面活性剤のほか、以下商品名で、KP341(信越化学工業社製)、ポリフローNo.75、同No.95(共栄社化学社製)、エフトップEF301、同EF303、同EF352(トーケムプロダクツ社製)、メガファックF171、同F173(大日本インキ化学工業社製)、フロラードFC430、同FC431(住友スリーエム社製)、アサヒガードAG710、サーフロンS-382、同SC-101、同SC-102、同SC-103、同SC-104、同SC-105、同SC-106(旭硝子社製)等が挙げられる。これらの界面活性剤は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
このような増感剤としては、カルバゾール類、アセトフェノン類、ベンゾフェノン類、ナフタレン類、フェノール類、ビアセチル、エオシン、ローズベンガル、ピレン類、アントラセン類、フェノチアジン類等が挙げられる。これらの増感剤は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
このような脂環族添加剤としては、1-アダマンタンカルボン酸、2-アダマンタノン、1-アダマンタンカルボン酸tert-ブチル、1-アダマンタンカルボン酸tert-ブトキシカルボニルメチル、1-アダマンタンカルボン酸α-ブチロラクトンエステル、1,3-アダマンタンジカルボン酸ジ-tert-ブチル、1-アダマンタン酢酸tert-ブチル、1-アダマンタン酢酸tert-ブトキシカルボニルメチル、1,3-アダマンタンジ酢酸ジ-tert-ブチル、2,5-ジメチル-2,5-ジ(アダマンチルカルボニルオキシ)ヘキサン等のアダマンタン誘導体類;デオキシコール酸tert-ブチル、デオキシコール酸tert-ブトキシカルボニルメチル、デオキシコール酸2-エトキシエチル、デオキシコール酸2-シクロヘキシルオキシエチル、デオキシコール酸3-オキソシクロヘキシル、デオキシコール酸テトラヒドロピラニル、デオキシコール酸メバロノラクトンエステル等のデオキシコール酸エステル類;リトコール酸tert-ブチル、リトコール酸tert-ブトキシカルボニルメチル、リトコール酸2-エトキシエチル、リトコール酸2-シクロヘキシルオキシエチル、リトコール酸3-オキソシクロヘキシル、リトコール酸テトラヒドロピラニル、リトコール酸メバロノラクトンエステル等のリトコール酸エステル類;アジピン酸ジメチル、アジピン酸ジエチル、アジピン酸ジプロピル、アジピン酸ジn-ブチル、アジピン酸ジtert-ブチル等のアルキルカルボン酸エステル類や、3-〔2-ヒドロキシ-2,2-ビス(トリフルオロメチル)エチル〕テトラシクロ[4.4.0.12,5.17,10]ドデカン等が挙げられる。これらの脂環族添加剤は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
また、染料又は顔料を配合することにより、露光部の潜像を可視化させて、露光時のハレーションの影響を緩和することができる。更に、接着助剤を配合することにより、レジスト膜と基板との接着性を改善することができる。
本発明の感放射線性組成物は、化学増幅型ポジ型レジスト膜を成膜可能な材料として有用である。
上記化学増幅型ポジ型レジスト膜においては、露光により感放射線性酸発生剤から発生した酸の作用によって、重合体中の酸解離性基が脱離し、重合体がアルカリ可溶性となる。即ち、レジスト膜に、アルカリ可溶性部位が生じる。このアルカリ可溶性部位は、レジストの露光部であり、この露光部はアルカリ現像液によって溶解、除去することができる。このようにして所望の形状のポジ型のレジストパターンを形成することができる。以下、具体的に説明する。
また、上記現像液のpHは、好ましくはpH8~pH14、より好ましくはpH9~pH14である。
上記有機溶剤としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトニルアセトン、シクロペンタノン、シクロヘキサノン、3-メチルシクロペンタノン、2,6-ジメチルシクロヘキサノン等のケトン類;メチルアルコール、エチルアルコール、n-プロピルアルコール、イソプロピルアルコール、n-ブチルアルコール、tert-ブチルアルコール、シクロペンタノール、シクロヘキサノール、1,4-ヘキサンジオール、1,4-ヘキサンジメチロール等のアルコール類;テトラヒドロフラン、ジオキサン等のエーテル類;酢酸エチル、酢酸n-ブチル、酢酸イソアミル等のエステル類;トルエン、キシレン等の芳香族炭化水素類;フェノール、ジメチルホルムアミド等が挙げられる。上記有機溶剤は、単独で用いてもよいし、2つ以上を組み合わせて用いてもよい。
上記現像液が、有機溶媒を含む場合、その含有量は、アルカリ性水溶液100体積部に対して、好ましくは100体積部以下である。この有機溶媒の含有量が100体積部を超えると、現像性が低下して、露光部の現像残りが多くなるおそれがある。
上記現像液で現像した後、通常、水洗及び乾燥が行われる。
尚、下記の実施例により得られた重合体のGPC分析及び13C-NMR分析の測定条件は、以下の通りである。
(1)重量平均分子量(Mw)及び数平均分子量(Mn)
東ソー社製GPCカラム(G2000HXL2本、G3000HXL1本及びG4000HXL1本)を用い、流量1.0ミリリットル/分、溶出溶剤テトラヒドロフラン、カラム温度40℃の条件で測定した。Mw及びMnは、単分散ポリスチレンを標準として求めた。また、分散度Mw/Mnは、両者のデータより算出した。
(2)13C-NMR分析
日本電子社製核磁気共鳴装置「JNM-EX270」(型式名)を用いて、測定した。
単量体合成例1
下記に示す化合物(X1)16.1g、メタクリル酸クロライド12.2g、及び1,4-ジアザビシクロ[2.2.2]オクタン13.12gを、塩化メチレン200gに溶解させた後、塩化メチレン還流下、6時間反応させた。反応終了後、反応母液に酢酸エチルを加え、有機層を水で洗浄した。その後、展開溶媒に酢酸エチル/n-ヘキサン=1/1(体積比)の混合溶媒を用いて、シリカゲルカラムクロマトグラフィーを行うことにより、下記に示す化合物(X-1-1)を得た(収率60%)。
上記化合物(X1)の代わりに、下記に示す各化合物(X2)~(X5)を用いた以外は、上記単量体合成例1と同様の方法により、下記に示す各化合物(X-1-2)~(X-1-5)を合成した。
重合体製造例1[重合体(A-1)の合成]
p-アセトキシスチレン5.5g、上記単量体合成例1で得られた化合物(X-1-1)4.5g、アゾビスイソブチロニトリル(以下、「AIBN」という)0.4g及びtert-ドデシルメルカプタン0.1gを、プロピレングリコールモノメチルエーテル10gに溶解した後、窒素雰囲気下、反応温度を70℃に保持して、16時間重合させた。重合後、反応溶液を500gのn-ヘキサン中に滴下して、生成共重合体を凝固精製した。次いで、この共重合体に、再度プロピレングリコールモノメチルエーテル7.5gを加え、更に、メタノール15g、トリエチルアミン4.0g及び水1.0gを加えて、65℃で、8時間加水分解反応を行った。反応後、溶剤及びトリエチルアミンを減圧留去し、得られた共重合体をアセトン10gに溶解した。そして、100gの水中に滴下して凝固させ、生成した白色粉末をろ過して、減圧下50℃で一晩乾燥した。
得られた共重合体は、Mwが10000、Mw/Mnが2.4であった。また、13C-NMR分析の結果、p-ヒドロキシスチレン及び化合物(X-1-1)に由来する各繰り返し単位の含有比(モル比)が66:34の共重合体であった。以下、この共重合体を、重合体(A-1)とする。
前記式(X-1-2)で表される化合物(以下、「化合物(X-1-2)」ともいう)54g、下記式(M-3)で表される化合物(以下、「化合物(M-3)」ともいう)46g、アゾビスイソブチロニトリル2gを、メチルエチルケトン300gに溶解した後、窒素雰囲気下、反応温度を78℃に保持して、6時間重合させた。重合後、反応溶液を2000gのメタノール中に滴下して、共重合体を凝固させ、次いで、この共重合体に、300gのメタノールで2回洗浄し、生成した白色粉末をろ過して、減圧下50℃で一晩乾燥した。
得られた共重合体は、Mwが8900、Mw/Mnが2.5であった。また、13C-NMR分析の結果、化合物(X-1-2)に由来する繰り返し単位及び化合物(M-3)に由来する繰り返し単位の含有比(モル比)が48:52の共重合体であった。以下、この共重合体を、重合体(A-2)とする。
化合物(X-1-1)の代わりに、上記単量体合成例2で得られた化合物(X-1-2)を用いたこと以外は、上記重合体製造例1と同様にして共重合体を製造した。
得られた共重合体は、Mwが12000、Mw/Mnが2.5であった。また、13C-NMR分析の結果、p-ヒドロキシスチレン及び化合物(X-1-2)に由来する各繰り返し単位の含有比(モル比)が67:33の共重合体であった。以下、この共重合体を、重合体(A-3)とする。
化合物(X-1-1)の代わりに、上記単量体合成例3で得られた化合物(X-1-3)を用いたこと以外は、上記重合体製造例1と同様にして共重合体を製造した。
得られた共重合体は、Mwが11000、Mw/Mnが2.6であった。また、13C-NMR分析の結果、p-ヒドロキシスチレン及び化合物(X-1-3)に由来する各繰り返し単位の含有比(モル比)が65:35の共重合体であった。以下、この共重合体を、重合体(A-4)とする。
化合物(X-1-1)の代わりに、上記単量体合成例4で得られた化合物(X-1-4)及び下記単量体(M-4)を用いたこと以外は、上記重合体製造例1と同様にして共重合体を製造した。
得られた共重合体は、Mwが12000、Mw/Mnが2.6であった。また、13C-NMR分析の結果、p-ヒドロキシスチレン、化合物(X-1-4)及び単量体(M-4)に由来する各繰り返し単位の含有比(モル比)が60:25:15の共重合体であった。以下、この共重合体を、重合体(A-5)とする。
化合物(X-1-1)の代わりに、上記単量体合成例5で得られた化合物(X-1-5)を用いたこと以外は、上記重合体製造例1と同様にして共重合体を製造した。
得られた共重合体は、Mwが11000、Mw/Mnが2.4であった。また、13C-NMR分析の結果、p-ヒドロキシスチレン、化合物(X-1-5)に由来する各繰り返し単位の含有比(モル比)が68:32の共重合体であった。以下、この共重合体を、重合体(A-6)とする。
p-アセトキシスチレン109.6g、下記に示す化合物(M-2)90.4g、AIBN6.8g及びtert-ドデシルメルカプタン2.6gを、プロピレングリコールモノメチルエーテル200gに溶解した後、窒素雰囲気下、反応温度を70℃に保持して、16時間重合させた。重合後、反応溶液を10000gのn-ヘキサン中に滴下して、生成共重合体を凝固精製した。次いで、この共重合体に、再度プロピレングリコールモノメチルエーテル150gを加え、更に、メタノール300g、トリエチルアミン80g及び水15gを加えて、65℃で、8時間加水分解反応を行った。反応後、溶剤及びトリエチルアミンを減圧留去し、得られた共重合体をアセトン200gに溶解した。そして、2000gの水中に滴下して凝固させ、生成した白色粉末をろ過して、減圧下50℃で一晩乾燥した。
得られた共重合体は、Mwが11000、Mw/Mnが2.1であった。また、13C-NMR分析の結果、p-ヒドロキシスチレンと化合物(M-2)に由来する各繰り返し単位の含有比(モル比)が65:35の共重合体であった。以下、この共重合体を、重合体(A-7)とする。
実施例1~15及び比較例1~2
上記で得られた重合体と、以下に示す成分とを、表1に示す割合で混合し、得られた混合液を孔径200nmのメンブランフィルターでろ過することにより、感放射線性組成物を製造した。
(A-1):重合体製造例1で得られた重合体(A-1)
(A-2):重合体製造例2で得られた重合体(A-2)
(A-3):重合体製造例3で得られた重合体(A-3)
(A-4):重合体製造例4で得られた重合体(A-4)
(A-5):重合体製造例5で得られた重合体(A-5)
(A-6):重合体製造例6で得られた重合体(A-6)
(A-7):比較用重合体製造例で得られた重合体(A-7)
(2)感放射線性酸発生剤(B)
(B-1):トリフェニルスルホニウムトリフルオロメタンスルホネート
(B-2):トリフェニルスルホニウムノナフルオロ-n-ブタンスルホネート
(B-3):トリフェニルスルホニウム1,1,2,2-テトラフルオロ-2-(テトラシクロ[4.4.0.12,5.17,10]ドデカン-8-イル)エタンスルホネート
(B-4):トリフェニルスルホニウム1,1-ジフルオロ-2-(ビシクロ[2.2.1]ヘプタン-2-イル)エタンスルホネート
(B-5):下記式(2x-16)で表される化合物
(B-7):下記式(2x-18)で表される化合物
(B-8):下記式(2x-19)で表される化合物
(C-1):トリ-n-オクチルアミン
(C-2):トリフェニルスルホニウムサリチレート
(C-3):N-tert-ブトキシカルボニル-2-フェニルベンズイミダゾール
(4)溶剤(D)
(D-1):乳酸エチル
(D-2):プロピレングリコールモノメチルエーテルアセテート
(D-3):シクロヘキサノン
東京エレクトロン社製の「クリーントラックACT-8」内で、シリコンウエハー上に感放射線性組成物をスピンコートした後、表2に示す条件でPB(加熱処理)を行い、膜厚60nmのレジスト被膜を形成した。その後、簡易型の電子線描画装置(日立製作所社製、型式「HL800D」、出力;50KeV、電流密度;5.0アンペア/cm2)を用いてレジスト被膜に電子線を照射した。電子線の照射後、表2に示す条件でPEBを行った。その後、2.38%テトラメチルアンモニウムヒドロキシド水溶液を用い、23℃で1分間、パドル法により現像した後、純水で水洗し、乾燥して、レジストパターンを形成した。このようにして形成したレジストについて、下記項目の評価を行った。
線幅150nmのライン部と、隣り合うライン部によって形成される間隔が150nmのスペース部(即ち、溝)と、からなるパターン(いわゆる、ライン・アンド・スペースパターン(1L1S))を1対1の線幅に形成する露光量を最適露光量とし、この最適露光量により感度を評価した。
図1は、ライン・アンド・スペースパターンの形状を模式的に示す平面図である。また、図2は、ライン・アンド・スペースパターンの形状を模式的に示す断面図である。但し、図1及び図2で示す凹凸は、実際より誇張している。
設計線幅150nmのライン・アンド・スペースパターン(1L1S)のラインパターンを、半導体用走査電子顕微鏡(高分解能FEB測長装置、商品名「S-9220」、日立製作所社製)にて観察した。観察された形状について、図1及び図2に示すように、シリコンウエハー1上に形成したレジスト膜のライン部2の横側面2aに沿って生じた凹凸の最も著しい箇所における線幅と、設計線幅150nmとの差「ΔCD」を、CD-SEM(日立ハイテクノロジーズ社製、「S-9220」)にて測定することにより、ナノエッジラフネスを評価した。
ライン・アンド・スペースパターン(1L1S)について、最適露光量により解像されるラインパターンの最小線幅(nm)を解像度とした。
2;レジストパターン
2a;レジストパターンの横側面
Claims (7)
- 下記一般式(1)で表される繰り返し単位を含むことを特徴とする重合体。
R2は置換若しくは非置換の炭素原子数6~22のアリール基であり、
Yは炭素原子であり、
XはYとともにヘテロ原子を含む環状構造を形成するのに必要な原子団であって、-X1Z1X2-を表し、Z1は-O-、-S-、-CO-、-COO-、-SO-若しくは-SO2-であり、X1及びX2は、互いに同一又は異なって、単結合、メチレン基又は炭素原子数2~25のアルキレン基であり、X1及びX2は置換基を有してもよく、X1及びX2はそれぞれに存在する炭素原子どうしが2価の基で結合されてもよい。) - 前記一般式(1)で表される繰り返し単位が、下記一般式(1-1)で表される繰り返し単位である請求項1に記載の重合体。
R1は水素原子、メチル基、フッ素原子又はトリフルオロメチル基であり、
R3は1価の有機基、ヒドロキシル基又はハロゲン原子であり、
Yは炭素原子であり、
XはYとともにヘテロ原子を含む環状構造を形成するのに必要な原子団であって、-X1Z1X2-を表し、Z1は-O-、-S-、-CO-、-COO-、-SO-若しくは-SO2-であり、X1及びX2は、互いに同一又は異なって、単結合、メチレン基又は炭素原子数2~25のアルキレン基であり、X1及びX2は置換基を有してもよく、X1及びX2はそれぞれに存在する炭素原子どうしが2価の基で結合されてもよい。) - 更に、下記一般式(2)で表される繰り返し単位、下記一般式(3)で表される繰り返し単位、下記一般式(4)で表される繰り返し単位、下記一般式(5)で表される繰り返し単位、及び、下記一般式(N)で表される繰り返し単位から選ばれた少なくとも1種を含む請求項1又は2に記載の重合体。
- 酸解離性基含有重合体(A)と、感放射線性酸発生剤(B)と、を含有する感放射線性組成物であって、
前記酸解離性基含有重合体(A)が、請求項1乃至3のいずれかに記載の重合体であることを特徴とする感放射線性組成物。 - 前記感放射線性酸発生剤(B)が、下記一般式(b1)で表される化合物である請求項4に記載の感放射線性組成物。
M+Z- (b1)
(式中、M+は1価のオニウムカチオンであり、Z-は下記一般式(9-1)又は(9-2)で表される1価のアニオンである。)
- 下記一般式(10)で表される化合物であることを特徴とする単量体。
R2は置換若しくは非置換の炭素原子数6~22のアリール基であり、
Yは炭素原子であり、
XはYとともにヘテロ原子を含む環状構造を形成するのに必要な原子団であって、-X1Z1X2-を表し、Z1は-O-、-S-、-CO-、-COO-、-SO-若しくは-SO2-であり、X1及びX2は、互いに同一又は異なって、単結合、メチレン基又は炭素原子数2~25のアルキレン基であり、X1及びX2は置換基を有してもよく、X1及びX2はそれぞれに存在する炭素原子どうしが2価の基で結合されてもよい。) - 下記一般式(10)で表される化合物の製造方法。
R2は置換若しくは非置換の炭素原子数6~22のアリール基であり、
Yは炭素原子であり、
XはYとともにヘテロ原子を含む環状構造を形成するのに必要な原子団であって、-X1Z1X2-を表し、Z1は-O-、-S-、-CO-、-COO-、-SO-若しくは-SO2-であり、X1及びX2は、互いに同一又は異なって、単結合、メチレン基又は炭素原子数2~25のアルキレン基であり、X1及びX2は置換基を有してもよく、X1及びX2はそれぞれに存在する炭素原子どうしが2価の基で結合されてもよい。)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020127005396A KR101706409B1 (ko) | 2009-09-30 | 2010-09-02 | 중합체, 감방사선성 조성물 및 단량체, 및 그의 제조 방법 |
JP2011534155A JP5609881B2 (ja) | 2009-09-30 | 2010-09-02 | 重合体及び感放射線性組成物並びに単量体 |
US13/427,855 US8389202B2 (en) | 2009-09-30 | 2012-03-22 | Polymer, radiation-sensitive composition, monomer, and method of producing compound |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009-228360 | 2009-09-30 | ||
JP2009228360 | 2009-09-30 | ||
JP2010-159097 | 2010-07-13 | ||
JP2010159097 | 2010-07-13 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/427,855 Continuation US8389202B2 (en) | 2009-09-30 | 2012-03-22 | Polymer, radiation-sensitive composition, monomer, and method of producing compound |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011040175A1 true WO2011040175A1 (ja) | 2011-04-07 |
Family
ID=43826003
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/065066 WO2011040175A1 (ja) | 2009-09-30 | 2010-09-02 | 重合体及び感放射線性組成物並びに単量体及びその製造方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US8389202B2 (ja) |
JP (1) | JP5609881B2 (ja) |
KR (1) | KR101706409B1 (ja) |
TW (1) | TWI485168B (ja) |
WO (1) | WO2011040175A1 (ja) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013061624A (ja) * | 2011-03-28 | 2013-04-04 | Fujifilm Corp | 感活性光線性又は感放射線性樹脂組成物、並びに、この組成物を用いた感活性光線性又は感放射線性膜及びパターン形成方法 |
JP2013068777A (ja) * | 2011-09-22 | 2013-04-18 | Fujifilm Corp | パターン形成方法、感活性光線性又は感放射線性樹脂組成物、レジスト膜、電子デバイスの製造方法及び電子デバイス |
JP2013200560A (ja) * | 2012-02-23 | 2013-10-03 | Tokyo Ohka Kogyo Co Ltd | レジスト組成物、レジストパターン形成方法 |
WO2015046021A1 (ja) * | 2013-09-26 | 2015-04-02 | Jsr株式会社 | 感放射線性樹脂組成物及びレジストパターン形成方法 |
JP2016133546A (ja) * | 2015-01-16 | 2016-07-25 | 東京応化工業株式会社 | レジスト組成物及びレジストパターン形成方法 |
US10101658B2 (en) | 2015-01-16 | 2018-10-16 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition and method of forming resist pattern |
KR20190039649A (ko) | 2017-10-05 | 2019-04-15 | 도오꾜오까고오교 가부시끼가이샤 | 레지스트 조성물, 레지스트 패턴 형성 방법, 고분자 화합물 및 화합물 |
KR20190063411A (ko) | 2017-11-29 | 2019-06-07 | 도오꾜오까고오교 가부시끼가이샤 | 레지스트 조성물, 레지스트 패턴 형성 방법, 고분자 화합물 및 화합물 |
US10324377B2 (en) | 2015-06-15 | 2019-06-18 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition and method of forming resist pattern |
JP7373059B2 (ja) | 2020-04-28 | 2023-11-01 | 富士フイルム株式会社 | 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、マスクブランクス、パターン形成方法及び電子デバイスの製造方法 |
US11829068B2 (en) | 2020-10-19 | 2023-11-28 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition, method of forming resist pattern, compound, and resin |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7115295B2 (ja) * | 2018-12-25 | 2022-08-09 | Jnc株式会社 | (メタ)アクリレート化合物、重合体、レジスト材料及び(メタ)アクリレート化合物の製造方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07325402A (ja) * | 1994-06-01 | 1995-12-12 | Fujitsu Ltd | レジスト及びパターン形成方法 |
JP2000231194A (ja) * | 1998-12-07 | 2000-08-22 | Fuji Photo Film Co Ltd | ポジ型フォトレジスト組成物 |
JP2002082439A (ja) * | 2000-06-22 | 2002-03-22 | Toray Ind Inc | ポジ型感放射線性組成物およびこれを用いたレジストパターンの製造方法 |
JP2002156760A (ja) * | 2000-11-20 | 2002-05-31 | Toray Ind Inc | ポジ型感放射線性組成物およびこれを用いたレジストパターンの製造方法 |
JP2002351080A (ja) * | 2001-05-28 | 2002-12-04 | Toray Ind Inc | ポジ型感放射線性組成物 |
JP2002372785A (ja) * | 2001-04-12 | 2002-12-26 | Toray Ind Inc | ポジ型感放射線性組成物およびこれを用いたレジストパターンの製造方法 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0612452B2 (ja) | 1982-09-30 | 1994-02-16 | ブリュ−ワ−・サイエンス・インコ−ポレイテッド | 集積回路素子の製造方法 |
EP0522990B1 (en) | 1991-06-28 | 1996-09-25 | International Business Machines Corporation | Top antireflective coating films |
US5561194A (en) | 1995-03-29 | 1996-10-01 | International Business Machines Corporation | Photoresist composition including polyalkylmethacrylate co-polymer of polyhydroxystyrene |
US6576392B1 (en) | 1996-12-07 | 2003-06-10 | Fuji Photo Film Co., Ltd. | Positive photoresist composition |
US6492086B1 (en) | 1999-10-08 | 2002-12-10 | Shipley Company, L.L.C. | Phenolic/alicyclic copolymers and photoresists |
JP2001166478A (ja) | 1999-12-03 | 2001-06-22 | Jsr Corp | 感放射線性樹脂組成物 |
JP2001166474A (ja) | 1999-12-03 | 2001-06-22 | Jsr Corp | 感放射線性樹脂組成物 |
EP1229390A4 (en) | 2000-06-22 | 2004-06-02 | Toray Industries | POSITIVE RADIOSENSITIVE COMPOSITION AND METHOD FOR PRODUCING STRUCTURES USING THE SAME |
US6838225B2 (en) * | 2001-01-18 | 2005-01-04 | Jsr Corporation | Radiation-sensitive resin composition |
JP4595275B2 (ja) | 2001-09-28 | 2010-12-08 | 住友化学株式会社 | 化学増幅型ポジ型レジスト組成物 |
TWI314943B (en) * | 2002-08-29 | 2009-09-21 | Radiation-sensitive resin composition | |
JP4765625B2 (ja) * | 2003-08-05 | 2011-09-07 | Jsr株式会社 | アクリル系重合体および感放射線性樹脂組成物 |
KR100944227B1 (ko) * | 2007-12-17 | 2010-02-24 | 제일모직주식회사 | 방향족 산 분해성 기를 갖는 (메타)아크릴레이트 화합물 및감광성 고분자 및 레지스트 조성물 |
EP2101217B1 (en) * | 2008-03-14 | 2011-05-11 | Shin-Etsu Chemical Co., Ltd. | Sulfonium salt-containing polymer, resist compositon, and patterning process |
JP5136792B2 (ja) * | 2008-11-21 | 2013-02-06 | 信越化学工業株式会社 | ポジ型レジスト材料及びパターン形成方法 |
TWI503334B (zh) * | 2009-02-19 | 2015-10-11 | Jsr Corp | 聚合物及敏輻射線性組成物、及單體 |
JP5655786B2 (ja) * | 2009-09-11 | 2015-01-21 | Jsr株式会社 | 感放射線性組成物 |
US8609319B2 (en) * | 2010-10-01 | 2013-12-17 | Jsr Corporation | Radiation-sensitive resin composition and resist film formed using the same |
-
2010
- 2010-09-02 JP JP2011534155A patent/JP5609881B2/ja active Active
- 2010-09-02 WO PCT/JP2010/065066 patent/WO2011040175A1/ja active Application Filing
- 2010-09-02 KR KR1020127005396A patent/KR101706409B1/ko active IP Right Grant
- 2010-09-29 TW TW099133038A patent/TWI485168B/zh active
-
2012
- 2012-03-22 US US13/427,855 patent/US8389202B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07325402A (ja) * | 1994-06-01 | 1995-12-12 | Fujitsu Ltd | レジスト及びパターン形成方法 |
JP2000231194A (ja) * | 1998-12-07 | 2000-08-22 | Fuji Photo Film Co Ltd | ポジ型フォトレジスト組成物 |
JP2002082439A (ja) * | 2000-06-22 | 2002-03-22 | Toray Ind Inc | ポジ型感放射線性組成物およびこれを用いたレジストパターンの製造方法 |
JP2002156760A (ja) * | 2000-11-20 | 2002-05-31 | Toray Ind Inc | ポジ型感放射線性組成物およびこれを用いたレジストパターンの製造方法 |
JP2002372785A (ja) * | 2001-04-12 | 2002-12-26 | Toray Ind Inc | ポジ型感放射線性組成物およびこれを用いたレジストパターンの製造方法 |
JP2002351080A (ja) * | 2001-05-28 | 2002-12-04 | Toray Ind Inc | ポジ型感放射線性組成物 |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013061624A (ja) * | 2011-03-28 | 2013-04-04 | Fujifilm Corp | 感活性光線性又は感放射線性樹脂組成物、並びに、この組成物を用いた感活性光線性又は感放射線性膜及びパターン形成方法 |
JP2013068777A (ja) * | 2011-09-22 | 2013-04-18 | Fujifilm Corp | パターン形成方法、感活性光線性又は感放射線性樹脂組成物、レジスト膜、電子デバイスの製造方法及び電子デバイス |
US9120288B2 (en) | 2011-09-22 | 2015-09-01 | Fujifilm Corporation | Pattern forming method, actinic ray-sensitive or radiation-sensitive resin composition, resist film, method for preparing electronic device, and electronic device |
JP2013200560A (ja) * | 2012-02-23 | 2013-10-03 | Tokyo Ohka Kogyo Co Ltd | レジスト組成物、レジストパターン形成方法 |
US9874816B2 (en) | 2013-09-26 | 2018-01-23 | Jsr Corporation | Radiation-sensitive resin composition and resist pattern-forming method |
WO2015046021A1 (ja) * | 2013-09-26 | 2015-04-02 | Jsr株式会社 | 感放射線性樹脂組成物及びレジストパターン形成方法 |
JPWO2015046021A1 (ja) * | 2013-09-26 | 2017-03-09 | Jsr株式会社 | 感放射線性樹脂組成物及びレジストパターン形成方法 |
US10101658B2 (en) | 2015-01-16 | 2018-10-16 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition and method of forming resist pattern |
JP2016133546A (ja) * | 2015-01-16 | 2016-07-25 | 東京応化工業株式会社 | レジスト組成物及びレジストパターン形成方法 |
US10324377B2 (en) | 2015-06-15 | 2019-06-18 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition and method of forming resist pattern |
KR20190039649A (ko) | 2017-10-05 | 2019-04-15 | 도오꾜오까고오교 가부시끼가이샤 | 레지스트 조성물, 레지스트 패턴 형성 방법, 고분자 화합물 및 화합물 |
US10908502B2 (en) | 2017-10-05 | 2021-02-02 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition, method of forming resist pattern, polymeric compound, and compound |
KR20190063411A (ko) | 2017-11-29 | 2019-06-07 | 도오꾜오까고오교 가부시끼가이샤 | 레지스트 조성물, 레지스트 패턴 형성 방법, 고분자 화합물 및 화합물 |
US11061329B2 (en) | 2017-11-29 | 2021-07-13 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition, method of forming resist pattern, polymeric compound, and compound |
JP7373059B2 (ja) | 2020-04-28 | 2023-11-01 | 富士フイルム株式会社 | 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、マスクブランクス、パターン形成方法及び電子デバイスの製造方法 |
US11829068B2 (en) | 2020-10-19 | 2023-11-28 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition, method of forming resist pattern, compound, and resin |
Also Published As
Publication number | Publication date |
---|---|
KR101706409B1 (ko) | 2017-02-13 |
JPWO2011040175A1 (ja) | 2013-02-28 |
US20120178024A1 (en) | 2012-07-12 |
JP5609881B2 (ja) | 2014-10-22 |
TW201118106A (en) | 2011-06-01 |
TWI485168B (zh) | 2015-05-21 |
KR20120088658A (ko) | 2012-08-08 |
US8389202B2 (en) | 2013-03-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5737174B2 (ja) | 重合体及び感放射線性組成物 | |
JP5609881B2 (ja) | 重合体及び感放射線性組成物並びに単量体 | |
JP5434906B2 (ja) | 感放射線性組成物及び重合体並びに単量体 | |
JP5578170B2 (ja) | 感放射線性樹脂組成物および重合体 | |
JP5660037B2 (ja) | 感放射線性樹脂組成物 | |
JP2009258598A (ja) | 感放射線性組成物及びパターン形成方法 | |
JP2010134126A (ja) | 感放射線性組樹脂組成物 | |
JP5678449B2 (ja) | 感放射線性組成物 | |
JP5092986B2 (ja) | 重合体及び感放射線性組成物並びに単量体 | |
JP5434323B2 (ja) | 感放射線性樹脂組成物及びスルホニウム塩 | |
JP5353434B2 (ja) | 感放射線性樹脂組成物 | |
JP5146212B2 (ja) | 感放射線性組成物 | |
JP5262631B2 (ja) | 感放射線性組成物 | |
JP2011059531A (ja) | 感放射線性樹脂組成物及びパターン形成方法 | |
JP2009198963A (ja) | 感放射線性組成物及び化合物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10820295 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2011534155 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20127005396 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 10820295 Country of ref document: EP Kind code of ref document: A1 |