WO2016181722A1 - パターン形成方法、電子デバイスの製造方法、及び、感活性光線性又は感放射線性樹脂組成物 - Google Patents
パターン形成方法、電子デバイスの製造方法、及び、感活性光線性又は感放射線性樹脂組成物 Download PDFInfo
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- WO2016181722A1 WO2016181722A1 PCT/JP2016/060983 JP2016060983W WO2016181722A1 WO 2016181722 A1 WO2016181722 A1 WO 2016181722A1 JP 2016060983 W JP2016060983 W JP 2016060983W WO 2016181722 A1 WO2016181722 A1 WO 2016181722A1
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- 125000002883 imidazolyl group Chemical group 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229930002839 ionone Natural products 0.000 description 1
- 150000002499 ionone derivatives Chemical class 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- SMEROWZSTRWXGI-HVATVPOCSA-N lithocholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 SMEROWZSTRWXGI-HVATVPOCSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- MKQLBNJQQZRQJU-UHFFFAOYSA-N morpholin-4-amine Chemical compound NN1CCOCC1 MKQLBNJQQZRQJU-UHFFFAOYSA-N 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical group C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 125000005574 norbornylene group Chemical group 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N octan-4-ol Chemical compound CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000010363 phase shift Effects 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000005562 phenanthrylene group Chemical group 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- SBMSLRMNBSMKQC-UHFFFAOYSA-N pyrrolidin-1-amine Chemical compound NN1CCCC1 SBMSLRMNBSMKQC-UHFFFAOYSA-N 0.000 description 1
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 150000003431 steroids Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LPSWFOCTMJQJIS-UHFFFAOYSA-N sulfanium;hydroxide Chemical compound [OH-].[SH3+] LPSWFOCTMJQJIS-UHFFFAOYSA-N 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000008027 tertiary esters Chemical group 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- BUGOPWGPQGYYGR-UHFFFAOYSA-N thiane 1,1-dioxide Chemical compound O=S1(=O)CCCCC1 BUGOPWGPQGYYGR-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- 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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- 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
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- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- 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
-
- 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
- G03F7/16—Coating processes; Apparatus therefor
-
- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/325—Non-aqueous compositions
-
- 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
-
- 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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
-
- 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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
-
- 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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
-
- 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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
Definitions
- the present invention relates to a pattern formation method, an electronic device manufacturing method, and an actinic ray-sensitive or radiation-sensitive resin composition. More specifically, the present invention relates to a pattern forming method suitable for a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal and a thermal head, and other photofabrication lithography processes, and an actinic ray used therein. Relates to a photosensitive or radiation-sensitive resin composition (resist composition). The present invention also relates to an electronic device manufacturing method including the pattern forming method.
- Patent Documents 1 and 2 disclose resist compositions containing a resin having a repeating unit in which a lactone ring is directly connected to the main chain.
- the inventors of the present invention formed a film (resist film) using the resist composition described in [Examples] of Patent Documents 1 and 2, and then used exposure and a developer containing an organic solvent. As a result, it was found that DOF may not meet the level required recently.
- the present invention has been made in view of the above points, and is a pattern forming method capable of obtaining a good DOF, a method for producing an electronic device including the pattern forming method, and an actinic ray-sensitive or radiation-sensitive resin composition.
- the purpose is to provide goods.
- the present inventors use a resin having a repeating unit in which the lactone ring is directly connected to the main chain and having a specific repeating unit at a specific content.
- the inventors have found that the DOF becomes large and completed the present invention.
- the present invention provides the following [1] to [13].
- [1] (i) a step of forming an actinic ray-sensitive or radiation-sensitive resin composition film on a substrate with an actinic ray-sensitive or radiation-sensitive resin composition, (ii) irradiating the film with actinic rays or radiation And (iii) a step of developing the film irradiated with the actinic ray or radiation with a developer containing an organic solvent, wherein the actinic ray sensitivity or
- the radiation-sensitive resin composition contains a resin P and a compound that generates an acid upon irradiation with actinic rays or radiation, and the resin P is a repeating unit Q1 represented by the general formula (q1) described below, and
- the pattern formation method which has repeating unit Q2 represented by general formula (q2) mentioned later, and content of the said repeating unit Q2 with respect to all the repeating units of the said resin P is 20 mol% or more.
- R 9 represents a polycyclic cycloalkyl group having 3 to 14 carbon atoms.
- R 9 represents a polycyclic cycloalkyl group having 3 to 14 carbon atoms.
- the resin P further includes a repeating unit having a lactone structure different from the repeating unit Q1.
- [5] The pattern forming method according to [4], wherein the content of the repeating unit Q2 with respect to all repeating units of the resin P is 50 mol% or more.
- the actinic ray-sensitive or radiation-sensitive resin composition having a repeating unit Q2 represented by (q2), wherein the content of the repeating unit Q2 with respect to all repeating units of the resin P is 20 mol% or more. .
- R 9 represents a polycyclic cycloalkyl group having 3 to 14 carbon atoms.
- a pattern forming method capable of obtaining good DOF
- an electronic device manufacturing method including the pattern forming method
- an actinic ray-sensitive or radiation-sensitive resin composition an actinic ray-sensitive or radiation-sensitive resin composition.
- an “alkyl group” that does not explicitly indicate substitution or unsubstituted includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). I will do it.
- active light or “radiation” means, for example, an emission line spectrum of a mercury lamp, a deep ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam, an ion beam or other particle beam. Means.
- light means actinic rays or radiation.
- exposure in the present specification is not limited to exposure to far ultraviolet rays, X-rays, extreme ultraviolet rays (EUV light) and the like represented by mercury lamps and excimer lasers. It is also assumed that drawing by particle beams such as.
- (meth) acrylate” means “at least one of acrylate and methacrylate”.
- (Meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the resin P contained in the actinic ray-sensitive or radiation-sensitive resin composition for forming the resist film is a repeating unit Q1 represented by the general formula (q1) described later, and will be described later. It has the repeating unit Q2 represented by the general formula (q2), and the content of the repeating unit Q2 with respect to all the repeating units of the resin P is 20 mol% or more.
- a large focus tolerance (DOF) can be obtained. The reason is not clear, but is presumed as follows.
- a resin having a repeating unit having a lactone structure has a glass transition temperature lowered by the action of an acid to reduce the rigidity, thereby making it easier for the acid to move and improving the acid diffusibility.
- the repeating unit Q1 represented by the general formula (q1) described later in which the lactone structure is directly bonded to the main chain has a larger glass transition temperature reduction amount than the repeating unit in which the lactone structure is not directly bonded to the main chain. It is considered that the acid diffusibility becomes better.
- the covalent bond between the oxygen atom and the quaternary carbon atom is broken by the action of an acid, and the protection includes a quaternary carbon atom.
- the group leaves.
- the detached protecting group does not volatilize immediately but remains in the resist film for a while and assists in acid diffusion.
- the content of the repeating unit Q2 is as large as 20 mol% or more, it is considered that the amount of the protecting group to be eliminated is increased and the acid diffusion is improved.
- the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as “the composition of the present invention” or “the resist composition of the present invention”) is irradiated with resin P and actinic rays or radiation. And a compound capable of generating an acid.
- the resin P has a repeating unit Q1 represented by the general formula (q1) described later and a repeating unit Q2 represented by the general formula (q2) described later, and all the repeating units of the resin P described above.
- the content of the repeating unit Q2 is 20 mol% or more.
- Such a composition of the present invention is used for negative development (development in which exposed portions remain as patterns and unexposed portions are removed). That is, development is performed using a developer containing an organic solvent.
- Resin P The resin P has at least a repeating unit Q1 represented by a general formula (q1) described later and a repeating unit Q2 represented by a general formula (q2) described later.
- Repeating unit Q1 The repeating unit Q1 is a repeating unit represented by the following general formula (q1).
- R 1 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.
- R 2 to R 5 each independently represents a hydrogen atom, a fluorine atom, a hydroxy group or an organic group having 1 to 20 carbon atoms.
- a represents an integer of 1 to 6.
- R 2 and R 3 , and R 4 and R 5 may be bonded to each other to form a ring structure having 3 to 10 ring members together with the carbon atom to which they are bonded.
- R 1 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.
- the organic group having 1 to 20 carbon atoms represented by R 1 in the general formula (q1) include a chain hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and carbon. Examples thereof include an aromatic hydrocarbon group having 6 to 20 atoms, a heterocyclic group having 3 to 10 ring members, an epoxy group, a cyano group, a carboxy group, and a group represented by —R′—QR ′′.
- R ′ is a single bond or a hydrocarbon group having 1 to 20 carbon atoms.
- R ′′ is an optionally substituted hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group having 3 to 10 ring members.
- Q is —O—, —CO—, —NH—, —SO 2 —, —SO— or a group formed by combining these.
- Some or all of the hydrogen atoms of the chain hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group are, for example, halogen atoms such as fluorine atoms; cyano groups, carboxy groups, hydroxy groups, thiol groups And a substituent such as a trialkylsilyl group;
- Examples of the chain hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a vinyl group, and an isopropenyl group.
- a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group are preferable, and a methyl group and an ethyl group are more preferable.
- Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclohexyl group, cyclooctyl group, and cyclodecyl group; norbornyl group And a polycyclic alicyclic hydrocarbon group such as an adamantyl group; Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.
- heterocyclic ring constituting the heterocyclic group having 3 to 10 ring members examples include lactone ring, cyclic carbonate, sultone ring, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine.
- a ring etc. are mentioned.
- a lactone ring, a cyclic carbonate, and a sultone ring are preferable, and a lactone ring is more preferable.
- Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ′ and R ′′ in —R′—QR ′′ include a chain hydrocarbon group having 1 to 20 carbon atoms, carbon number 3 And an alicyclic hydrocarbon group having 20 to 20 and an aromatic hydrocarbon group having 6 to 20 carbon atoms.
- the same groups as those exemplified as the organic group having 1 to 20 carbon atoms represented by R 1 can be mentioned.
- the description of the heterocyclic group having 3 to 10 ring members represented by R 1 can be applied to the heterocyclic group having 3 to 10 ring members represented by R ′′.
- R 1 is preferably a hydrogen atom from the viewpoint of the copolymerizability of the monomer giving the repeating unit Q1.
- R 2 to R 5 each independently represents a hydrogen atom, a fluorine atom, a hydroxy group, or an organic group having 1 to 20 carbon atoms.
- Specific examples and preferred embodiments of the organic group having 1 to 20 carbon atoms represented by R 2 to R 5 in formula (q1) include those having 1 to 20 carbon atoms represented by R 1 in formula (q1) described above. Same as organic group.
- R 2 and R 3 , and R 4 and R 5 may be bonded to each other to form a ring structure having 3 to 10 ring members together with the carbon atom to which they are bonded.
- the ring structure having 3 to 10 ring members that R 2 and R 3 , and R 4 and R 5 may be formed together with the carbon atom to which they are bonded include, for example, cyclopropane , Cyclopentane, cyclohexane, norbornane, alicyclic structure having an alicyclic ring such as adamantane; heterocyclic structure having a ring containing a hetero atom; Examples of the heterocyclic structure having a ring containing a hetero atom include a heterocyclic structure having a cyclic ether, a lactone ring, or a sultone ring, and other specific examples include tetrahydrofuran, tetrahydropyran, ⁇ -butyrolactone,
- R 2 and R 3 , and R 4 and R 5 are bonded to each other, and “ring structure” in the ring structure having 3 to 10 ring members that may be formed together with the carbon atom to which they are bonded.
- R 2 and R 3, and R 4 and R 5 is the bond when bonded to each other, but are not limited to bonds via chemical reactions.
- a represents an integer of 1 to 6.
- a is preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.
- the plurality of R 2 and R 3 may be the same or different.
- R 2 and R 3 are preferably a hydrogen atom or a chain hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.
- R 4 and R 5 are each a hydrogen atom, a chain hydrocarbon group having 1 to 20 carbon atoms, or a heterocyclic group having 3 to 10 ring members, or bonded to each other and bonded to each other. It is preferable to form a ring structure having 3 to 10 ring members together with the carbon atoms.
- repeating unit Q1 represented by the general formula (q1) examples include, but are not limited to, repeating units represented by the following formula.
- R 1 in formula has the same meaning as R 1 in the general formula (q1).
- the repeating unit Q1 represented by the general formula (q1) may be used alone or in combination of two or more.
- the content of the repeating unit Q1 represented by the general formula (q1) with respect to all the repeating units of the resin P is not particularly limited, but is preferably 5 to 60% by mole, more preferably 5 to 50% by mole. More preferred is mol%.
- repeating unit Q2 is a repeating unit represented by the following general formula (q2), which is usually decomposed by the action of an acid, the covalent bond between the oxygen atom and the quaternary carbon atom is cleaved, and a carboxy group is removed. Arise.
- R 6 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.
- R 7 and R 8 represent a chain alkyl group that may contain a branched structure having 1 to 10 carbon atoms.
- R 9 represents an alkyl group which may contain a branched structure having 1 to 10 carbon atoms or a monocyclic or polycyclic cycloalkyl group having 3 to 14 carbon atoms.
- two of R 7 to R 9 are not bonded to each other to form a ring structure.
- R 6 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.
- Specific examples and preferred embodiments of the organic group having 1 to 20 carbon atoms represented by R 6 in general formula (q2) include the organic group having 1 to 20 carbon atoms represented by R 1 in general formula (q1) described above. The same.
- R 6 is preferably a hydrogen atom or a chain hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a methyl group.
- R 7 and R 8 represent a chain alkyl group that may contain a branched structure having 1 to 10 carbon atoms.
- Examples of the chain alkyl group that may contain a branched structure having 1 to 10 carbon atoms represented by R 7 and R 8 in the general formula (q2) include a methyl group, an ethyl group, an n-propyl group, and iso-propyl.
- R 9 represents an alkyl group which may contain a branched structure having 1 to 10 carbon atoms or a monocyclic or polycyclic cycloalkyl group having 3 to 14 carbon atoms.
- alkyl group that may contain a branched structure having 1 to 10 carbon atoms represented by R 9 in the general formula (q2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and isobutyl. Group, tert-butyl group, n-hexyl group, n-octyl group and the like.
- the monocyclic or polycyclic cycloalkyl group having 3 to 14 carbon atoms represented by R 9 in the general formula (q2) is, for example, a monocyclic group having 3 to 14 carbon atoms such as a cyclopentyl group or a cyclohexyl group.
- a cycloalkyl group a polycyclic cycloalkyl group having 3 to 14 carbon atoms such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group; Are preferred, and an adamantyl group is more preferred.
- R 9 is preferably a monocyclic or polycyclic cycloalkyl group having 3 to 14 carbon atoms, and more preferably a polycyclic cycloalkyl group having 3 to 14 carbon atoms.
- Examples of the repeating unit Q2 represented by the general formula (q2) include, but are not limited to, repeating units represented by the following formula.
- Xa 1 in formula has the same meaning as R 6 in the general formula (q2).
- R 6 ⁇ R 8 in the formula have the same meanings as R 6 ⁇ R 8 in the general formula (q2).
- the repeating unit Q2 represented by the general formula (q2) may be used alone or in combination of two or more.
- the content of the repeating unit Q2 represented by the general formula (q2) with respect to all the repeating units of the resin P is 20 mol% or more.
- DOF is excellent.
- LWR is improved.
- the content of the repeating unit Q2 represented by the general formula (q2) with respect to all the repeating units of the resin P is preferably 40 mol% or more, and more preferably 50 mol% or more, from the reason that DOF and LWR become better. More preferred. On the other hand, although an upper limit is not specifically limited, For example, it is 80 mol% or less.
- the total content of the repeating unit Q1 represented by the general formula (q1) and the repeating unit Q2 represented by the general formula (q2) with respect to all the repeating units of the resin P is 25 mol% to 100 mol%. It is preferably 30 mol% to 100 mol%, more preferably 40 mol% to 100 mol%, and particularly preferably 50 mol% to 100 mol%.
- the resin P may further have a repeating unit Q3.
- the repeating unit Q3 is a repeating unit represented by the following general formula (q3) and is different from the repeating unit Q2 represented by the above general formula (q2).
- the repeating unit Q3 is usually decomposed by the action of an acid, and the covalent bond between the oxygen atom and the quaternary carbon atom is broken to generate a carboxy group.
- R 62 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.
- R 72 and R 82 represent a chain alkyl group which may contain a branched structure having 1 to 10 carbon atoms.
- R 92 represents an alkyl group which may contain a branched structure having 1 to 10 carbon atoms or a monocyclic or polycyclic cycloalkyl group having 3 to 14 carbon atoms.
- Specific examples and preferred embodiments of R 62 in general formula (q3) are the same as R 6 in general formula (q2) described above.
- R 72 ⁇ R 92 in the general formula (q3) except that no form two members to ring structure of R 72 ⁇ R 92 are each, above-mentioned general formula ( The same as R 7 to R 9 in q2).
- R 72 to R 92 may be bonded to each other to form a ring structure together with the carbon atom to which they are bonded, and have 3 to 20 carbon atoms.
- a ring structure is preferably formed, and a ring structure having 3 to 14 carbon atoms is more preferably formed.
- the ring structure include a monocyclic ring structure such as a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, a cyclooctyl group, and a cyclodecyl group; a polycyclic ring structure such as a norbornyl group and an adamantyl group; It is done.
- repeating unit Q3 includes the repeating unit represented by the general formula (q31) and the repeating unit represented by the general formula (q32) shown below.
- R 62 and R 92 of the general formula (q3) have the same meanings as R 62 and R 92 in, m is an integer of 1-8, an integer of 1 to 4 is preferred.
- R 62 has the same meaning as R 62 in the general formula (q3).
- R 789 represents a ring structure.
- the ring structure represented by R 789 is preferably a ring structure having 3 to 20 carbon atoms, more preferably a ring structure having 3 to 14 carbon atoms, and examples thereof include polycyclic ring structures such as a norbornyl group and an adamantyl group.
- the repeating unit Q3 may be used alone or in combination of two or more.
- the content of the repeating unit Q3 with respect to all the repeating units of the resin P is preferably 50 mol% or less, and more preferably 40 mol% or less. Although a minimum is not specifically limited, For example, it is 10 mol% or more.
- Repeating Unit Having Lactone Structure Resin P further contains a repeating unit having a lactone structure different from the above-mentioned repeating unit Q1 (hereinafter simply referred to as “repeating unit having a lactone structure” or “repeating unit (a)”. ").
- the repeating unit (a) is preferably a repeating unit derived from a (meth) acrylic acid derivative monomer.
- the repeating unit (a) may be used alone or in combination of two or more, but is preferably used alone.
- the content of the repeating unit (a) with respect to all the repeating units of the resin P depends on the structure of the repeating unit (a), but is 3 to 80 mol%, for example, and 3 to 60 mol%. preferable.
- the lactone structure is preferably a 5- to 7-membered lactone structure, and a structure in which another ring structure is condensed in a form of forming a bicyclo structure or a spiro structure on the 5- to 7-membered lactone structure is preferable.
- Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-8), and (LC1-4) is more preferred.
- the lactone structure portion may or may not have a substituent (Rb 2 ).
- Preferred substituents (Rb 2 ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, and carboxyl groups. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferred are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group.
- n 2 represents an integer of 0 to 4. When n 2 is 2 or more, a plurality of substituents (Rb 2 ) may be the same or different, and a plurality of substituents (Rb 2 ) may be bonded to form a ring. .
- Resin P may have a repeating unit having a sultone (cyclic sulfonate ester) structure (hereinafter also referred to as “repeating unit (b)”).
- the repeating unit (b) is preferably a repeating unit derived from a (meth) acrylic acid derivative monomer.
- the repeating unit (b) may be used alone or in combination of two or more, but is preferably used alone.
- the content of the repeating unit (b) with respect to all the repeating units of the resin P depends on the structure of the repeating unit (b), but is 3 to 80 mol%, for example, and 3 to 60 mol%. preferable.
- the sultone structure is preferably a 5- to 7-membered sultone structure, and a structure in which another ring structure is condensed in a form of forming a bicyclo structure or a spiro structure on the 5- to 7-membered sultone structure is preferable.
- the sultone structure portion may or may not have a substituent (Rb 2 ).
- the substituent (Rb 2) and n 2 have the same meanings as substituent (Rb 2) and n 2 of the portion of the lactone structure as described above.
- the resin P preferably contains a repeating unit having a sultone structure represented by the following general formula (III ′).
- R 82 in the formula (III ′) represents a monovalent organic group having a sultone structure.
- the monovalent organic group having a sultone structure represented by R 82 is not limited as long as it has a sultone structure.
- the general formulas (SL1-1) and (SL1-2) described above are used. The sultone structure represented by these is mentioned. Further, n 2 in (SL1-1) and (SL1-2) is more preferably 2 or less.
- R 82 is preferably a monovalent organic group having an unsubstituted sultone structure or a monovalent organic group having a sultone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent.
- a monovalent organic group having a sultone structure (cyano sultone) is more preferable.
- Resin P may have a repeating unit having a carbonate structure.
- the carbonate structure (cyclic carbonate structure) is a structure having a ring including a bond represented by —O—C ( ⁇ O) —O— as an atomic group constituting the ring.
- the ring containing a bond represented by —O—C ( ⁇ O) —O— as the atomic group constituting the ring is preferably a 5- to 7-membered ring, and most preferably a 5-membered ring. Such a ring may be condensed with another ring to form a condensed ring.
- the resin P preferably contains a repeating unit represented by the following general formula (A-1) as a repeating unit having a carbonate structure (cyclic carbonate structure).
- R A 1 represents a hydrogen atom or an alkyl group.
- R A 19 each independently represents a hydrogen atom or a chain hydrocarbon group.
- A represents a single bond, a divalent or trivalent chain hydrocarbon group, a divalent or trivalent alicyclic hydrocarbon group, or a divalent or trivalent aromatic hydrocarbon group, and A represents a trivalent
- the carbon atom contained in A and the carbon atom constituting the cyclic carbonate are combined to form a ring structure.
- n A represents an integer of 2 to 4.
- R A 1 represents a hydrogen atom or an alkyl group.
- the alkyl group represented by R A 1 may have a substituent such as a fluorine atom.
- R A 1 preferably represents a hydrogen atom, a methyl group or a trifluoromethyl group, and more preferably represents a methyl group.
- R A 19 each independently represents a hydrogen atom or a chain hydrocarbon group.
- the chain hydrocarbon group represented by R A 19 is preferably a chain hydrocarbon group having 1 to 5 carbon atoms.
- chain hydrocarbon group having 1 to 5 carbon atoms examples include linear alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, propyl group and butyl group; isopropyl group, isobutyl group, t A branched alkyl group having 3 to 5 carbon atoms such as a butyl group;
- the chain hydrocarbon group may have a substituent such as a hydroxyl group.
- R A 19 represents a hydrogen atom.
- the repeating unit (A-1a) described below is an example of a 5-membered ring structure
- (A-1j) is an example of a 6-membered ring structure.
- n A is preferably 2 or 3, and more preferably 2.
- A represents a single bond, a divalent or trivalent chain hydrocarbon group, a divalent or trivalent alicyclic hydrocarbon group, or a divalent or trivalent aromatic hydrocarbon.
- the divalent or trivalent chain hydrocarbon group is preferably a divalent or trivalent chain hydrocarbon group having 1 to 30 carbon atoms.
- the divalent or trivalent alicyclic hydrocarbon group is preferably a divalent or trivalent alicyclic hydrocarbon group having 3 to 30 carbon atoms.
- the divalent or trivalent aromatic hydrocarbon group is preferably a divalent or trivalent aromatic hydrocarbon group having 6 to 30 carbon atoms.
- chain hydrocarbon group means a hydrocarbon group composed only of a chain structure without including a cyclic structure in the main chain.
- chain hydrocarbon group having 1 to 30 carbon atoms include, for example, a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a tetramethylene group, and a pentamethylene group.
- A is a chain hydrocarbon group
- R A 1 is bonded to the ⁇ -position constituting the polymer.
- examples include a structure in which a carbon atom constituting a cyclic carbonate is bonded via a linear alkylene group having 1 to 5 carbon atoms (repeating units (A-1a) to (A-1f described later) )).
- a cyclic structure may be included as a substituent of A (repeating unit (A-1p) described later).
- the carbon atom contained in A and the carbon atom which comprises cyclic carbonate may be couple
- the cyclic carbonate may form part of a condensed ring or a spiro ring.
- a fused ring is formed when the ring structure contains two carbon atoms in the cyclic carbonate, and a spiro ring is formed when only one carbon atom in the cyclic carbonate is contained.
- (A-1g), (A-1q), (A-1t), (A-1u), (A-1i), (A-1r), (A-1s), (A-1v) described later ), (A-1w) is an example in which a condensed ring containing the carbon atom contained in A and the two carbon atoms constituting the cyclic carbonate is formed.
- the repeating unit (A-1j) described later is an example in which a spiro ring is formed by the carbon atom contained in A and one carbon atom constituting the cyclic carbonate.
- the ring structure may be a heterocyclic ring (repeating units (A-1q to A-1v described later)).
- alicyclic hydrocarbon group means a hydrocarbon group containing only an alicyclic hydrocarbon structure and no aromatic ring structure as the ring structure. However, it is not necessary to be constituted only by the structure of the alicyclic hydrocarbon, and a part thereof may include a chain structure.
- Examples of the “divalent alicyclic hydrocarbon group” include 1,3-cyclobutylene group, 1,3-cyclopentylene group, 1,4-cyclohexylene group, 1,5-cyclooctylene group, etc.
- a monocyclic cycloalkylene group having 3 to 10 carbon atoms such as 1,4-norbornylene group, 2,5-norbornylene group, 1,5-adamantylene group, 2,6-adamantylene group, etc.
- Examples of the “trivalent alicyclic hydrocarbon group” include a group in which one hydrogen atom is eliminated from the functional group.
- A is an alicyclic hydrocarbon group
- R A 1 is bonded to the ⁇ -position constituting the polymer.
- R A 1 is bonded via a cyclopentylene group (repeated units (A-1g) and (A-1h) described later) and a norbornylene group.
- repeating units (A-1k) and (A-1l) described later are examples in which a condensed ring containing a carbon atom contained in A and two carbon atoms constituting a cyclic carbonate is formed.
- repeating units (A-1j) and (A-1n) described later are examples in which a spiro ring is formed by the carbon atom contained in A and one carbon atom constituting the cyclic carbonate.
- aromatic hydrocarbon group means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic hydrocarbon structure.
- divalent aromatic hydrocarbon group examples include arylene groups such as a phenylene group, a tolylene group, a naphthylene group, a phenanthrylene group, and an anthrylene group.
- trimvalent aromatic hydrocarbon group examples include a group in which one hydrogen atom is eliminated from the functional group.
- A is an aromatic hydrocarbon group
- alkyl) acrylic acid typically (meth) acrylic acid
- R A 1 is bonded to the ⁇ -position constituting the polymer.
- examples thereof include those in which the carbon atom constituting the ester is bonded via a benzylene group (repeating unit (A-1o) described later).
- the repeating unit (A-1o) is an example in which a condensed ring including a carbon atom contained in A and two carbon atoms constituting a cyclic carbonate is formed.
- A preferably represents a divalent or trivalent chain hydrocarbon group or a divalent or trivalent alicyclic hydrocarbon group, and more preferably represents a divalent or trivalent chain hydrocarbon group. More preferably, it represents a linear alkylene group having 1 to 5 carbon atoms.
- repeating unit represented by formula (A-1) (repeating units (A-1a) to (A-1w)) are shown below, but the present invention is not limited thereto.
- R A 1 in the following specific examples are the same meaning as R A 1 in the general formula (A-1).
- one type of repeating units represented by the general formula (A-1) may be contained alone, or two or more types may be contained.
- the content of the repeating unit having a carbonate structure (cyclic carbonate structure) (preferably, the repeating unit represented by the general formula (A-1)) is based on the total repeating units constituting the resin P. It is preferably 3 to 80 mol%, more preferably 3 to 60 mol%, still more preferably 3 to 30 mol%.
- the resin P may contain other repeating units.
- the resin P may include a repeating unit having a hydroxyl group or a cyano group. Examples of such repeating units include the repeating units described in paragraphs ⁇ 0081> to ⁇ 0084> of JP-A No. 2014-089921. Further, the resin P may have a repeating unit having an alkali-soluble group.
- alkali-soluble group examples include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol (for example, a hexafluoroisopropanol group) in which the ⁇ -position is substituted with an electron withdrawing group.
- the repeating unit having an alkali-soluble group include the repeating units described in paragraphs ⁇ 0085> to ⁇ 0086> of JP-A No. 2014-098921.
- the resin P can further have a repeating unit that has an alicyclic hydrocarbon structure having no polar group (for example, an alkali-soluble group, a hydroxyl group, a cyano group, etc.) and does not exhibit acid decomposability.
- a repeating unit that has an alicyclic hydrocarbon structure having no polar group (for example, an alkali-soluble group, a hydroxyl group, a cyano group, etc.) and does not exhibit acid decomposability.
- repeating units include the repeating units described in paragraphs ⁇ 0114> to ⁇ 0123> of JP-A-2014-106299.
- the resin P may contain repeating units described in paragraphs ⁇ 0045> to ⁇ 0065> of JP2009-258586A, for example.
- the resin P used in the composition of the present invention can have various repeating units in addition to the above repeating units.
- Such a repeating unit examples include, but are not limited to, repeating units corresponding to the following monomers.
- a monomer for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.
- any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.
- the content molar ratio of each repeating structural unit is appropriately set.
- the resin P is not particularly limited as long as it has the repeating unit Q1 and the repeating unit Q2, and the content of the repeating unit Q2 is 20 mol% or more. It is preferable to have a repeating unit having a lactone structure different from Q1. More preferably, the resin P is preferably a resin composed only of the repeating unit Q1, the repeating unit Q2, and the repeating unit having a lactone structure different from the repeating unit Q1.
- the resin P used in the composition of the present invention has substantially no aromatic group from the viewpoint of transparency to ArF light. More specifically, the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally 0 mol during the entire repetition of the resin P. %, That is, it is more preferable not to have a repeating unit having an aromatic group.
- the resin P preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
- resin P does not contain a fluorine atom and a silicon atom from a compatible viewpoint with hydrophobic resin (D) mentioned later.
- the resin P used in the composition of the present invention is preferably a resin in which all repeating units are composed of (meth) acrylate-based repeating units.
- a resin in which all repeating units are methacrylate-based repeating units, a resin in which all repeating units are acrylate-based repeating units, and a resin in which all repeating units are methacrylate-based repeating units and acrylate-based repeating units are used.
- the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units.
- the resin P in the present invention can be synthesized according to a conventional method (for example, radical polymerization).
- a conventional method for example, radical polymerization
- a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours.
- the dropping polymerization method is added, and the dropping polymerization method is preferable.
- reaction solvent examples include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; amide solvents such as dimethylformamide and dimethylacetamide; And the like used in the composition of the present invention, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone. More preferably, the polymerization is performed using the same solvent as the solvent used in the composition of the present invention. Thereby, generation
- the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
- a polymerization initiator a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization.
- azo initiator an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is more preferable.
- Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like.
- an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery.
- the concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass.
- the reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 to 100 ° C.
- the weight average molecular weight (Mw) of the resin P is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3,000 to 15,000, particularly preferably 3 , 1,000 to 11,000.
- the degree of dispersion (molecular weight distribution) which is the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in the resin P is usually 1.0 to 3.0, preferably 1.0.
- the range is from 2.6 to 2.6, more preferably from 1.0 to 2.0, and even more preferably from 1.1 to 2.0.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined by gel permeation chromatography (GPC: Gel Permeation Chromatography) method using HLC-8120 (manufactured by Tosoh Corporation). It is a polystyrene conversion value.
- GPC Gel Permeation Chromatography
- HLC-8120 manufactured by Tosoh Corporation
- TSK gel Multipore HXL-M manufactured by Tosoh Corporation, 7.8 mm ID ⁇ 30.0 cm
- THF tetrahydrofuran
- the content of the resin P in the entire composition is preferably 30 to 99% by mass, more preferably 50 to 95% by mass in the total solid content.
- resin P may be used individually by 1 type, and may use 2 or more types together.
- composition of the present invention contains a compound that generates acid upon irradiation with actinic ray or radiation (hereinafter also referred to as “acid generator”). Although it does not specifically limit as an acid generator, It is preferable that it is a compound which generate
- the acid generator photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, irradiation of actinic ray or radiation used for micro resist, etc.
- Known compounds that generate an acid and mixtures thereof can be appropriately selected and used.
- compounds described in paragraphs ⁇ 0039> to ⁇ 0103> of JP-A-2010-61043 examples thereof include compounds described in paragraphs ⁇ 0284> to ⁇ 0389> of Kaikai 2013-4820, but the present invention is not limited thereto.
- Examples include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.
- produces an acid by irradiation of the actinic ray or radiation represented by following General formula (3) suitably is mentioned, for example. it can.
- Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
- R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when there are a plurality of R 4 and R 5 , R 4 and R 5 are the same But it can be different.
- L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
- W represents an organic group containing a cyclic structure. o represents an integer of 1 to 3.
- p represents an integer of 0 to 10.
- q represents an integer of 0 to 10.
- Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
- the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
- the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
- Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
- Xf is more preferably a fluorine atom or CF 3 . In particular, it is preferable that both Xf are fluorine atoms.
- R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when there are a plurality of R 4 and R 5 , R 4 and R 5 are the same But it can be different.
- the alkyl group as R 4 and R 5 may have a substituent, and preferably has 1 to 4 carbon atoms.
- R 4 and R 5 are preferably a hydrogen atom.
- Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in formula (3).
- L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
- the divalent linking group include —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —S—, —SO—, —SO 2 —, an alkylene group ( Preferable examples include 1 to 6 carbon atoms, a cycloalkylene group (preferably 3 to 10 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), or a divalent linking group obtained by combining a plurality of these.
- —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —SO 2 —, —COO-alkylene group—, —OCO-alkylene group—, —CONH— alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable.
- W represents an organic group containing a cyclic structure.
- a cyclic organic group is preferable.
- the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
- the alicyclic group may be monocyclic or polycyclic.
- the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
- polycyclic alicyclic group examples include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
- an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, is a PEB (heating after exposure) step. From the viewpoints of suppressing diffusibility in the film and improving MEEF (Mask Error Enhancement Factor).
- the aryl group may be monocyclic or polycyclic.
- Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. Among these, a naphthyl group having a relatively low light absorbance at 193 nm is preferable.
- the heterocyclic group may be monocyclic or polycyclic, but the polycyclic group can suppress acid diffusion more. Moreover, the heterocyclic group may have aromaticity or may not have aromaticity.
- heterocyclic ring having aromaticity examples include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring.
- heterocyclic ring that does not have aromaticity examples include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
- heterocyclic ring in the heterocyclic group a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable.
- lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the aforementioned resin P.
- the cyclic organic group may have a substituent.
- substituents include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), and a cycloalkyl group (monocyclic, polycyclic or spirocyclic).
- alkyl group which may be linear or branched, preferably 1 to 12 carbon atoms
- a cycloalkyl group monocyclic, polycyclic or spirocyclic.
- Well preferably having 3 to 20 carbon atoms
- aryl group preferably having 6 to 14 carbon atoms
- hydroxyl group alkoxy group
- ester group amide group, urethane group, ureido group, thioether group, sulfonamide group, and sulfonic acid
- An ester group is mentioned.
- the carbon constituting the cyclic organic group may be a carbonyl carbon.
- o represents an integer of 1 to 3.
- p represents an integer of 0 to 10.
- q represents an integer of 0 to 10.
- Xf is preferably a fluorine atom
- R 4 and R 5 are preferably both hydrogen atoms
- W is preferably a polycyclic hydrocarbon group.
- o is more preferably 1 or 2, and still more preferably 1.
- p is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.
- W is more preferably a polycyclic cycloalkyl group, and further preferably an adamantyl group or a diamantyl group.
- X + represents a cation.
- X + is not particularly limited as long as it is a cation, and preferred embodiments include, for example, cations (parts other than Z ⁇ ) in the general formula (ZI), (ZII) or (ZIII) described later.
- R 201 , R 202 and R 203 each independently represents an organic group.
- the organic group as R 201 , R 202 and R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
- Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
- Examples of the group formed by combining two members out of R 201 to R 203 include an alkylene group (eg, butylene group, pentylene group).
- Z ⁇ represents an anion in the general formula (3), and specifically represents the following anion.
- Examples of the organic group represented by R 201 , R 202 and R 203 include a corresponding group in the compound (ZI-4) described later.
- the compound which has two or more structures represented by general formula (ZI) may be sufficient.
- at least one of R 201 to R 203 of the compound represented by the general formula (ZI) is a single bond or at least one of R 201 to R 203 of the other compound represented by the general formula (ZI). It may be a compound having a structure bonded through a linking group.
- compound (ZI-4) As more preferred (ZI) component, for example, compound (ZI-4) described below can be mentioned.
- the compound (ZI-4) is represented by the following general formula (ZI-4).
- R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent.
- R 14 is independently a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group, when a plurality of R 14 are present.
- R 15 each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent.
- Two R 15 may be bonded to each other to form a ring.
- the ring skeleton may contain a hetero atom such as an oxygen atom or a nitrogen atom.
- it is preferred that two R 15 are alkylene groups and are bonded to each other to form a ring structure.
- l represents an integer of 0-2.
- r represents an integer of 0 to 8.
- Z ⁇ represents an anion in the general formula (3), specifically as described above.
- the alkyl group of R 13 , R 14 and R 15 is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, n -Butyl group, t-butyl group and the like are preferable.
- Examples of the cation of the compound represented by the general formula (ZI-4) in the present invention include paragraphs ⁇ 0121>, ⁇ 0123>, ⁇ 0124> of JP 2010-256842 A, and JP 2011-76056 A. The cations described in paragraphs ⁇ 0127>, ⁇ 0129>, ⁇ 0130>, etc.
- R 204 to R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
- the aryl group of R 204 to R 207 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
- the aryl group of R 204 to R 207 may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
- Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
- the alkyl group and cycloalkyl group in R 204 to R 207 are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups having a number of 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).
- the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have a substituent.
- substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have include an alkyl group (eg, having 1 to 15 carbon atoms) and a cycloalkyl group (eg, having 3 to 15 carbon atoms). ), Aryl groups (for example, having 6 to 15 carbon atoms), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups, and the like.
- Z ⁇ represents an anion in the general formula (3), specifically as described above.
- the acid generator (including a specific acid generator; the same shall apply hereinafter) may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.
- the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
- the acid generator may be incorporated in a part of the resin P described above, or may be incorporated in a resin different from the resin P.
- the acid generator can be synthesized by a known method, for example, according to the method described in JP-A No. 2007-161707.
- An acid generator can be used individually by 1 type or in combination of 2 or more types.
- the content of the acid generator in the composition (when there are a plurality of types) is preferably 0.1 to 30% by mass, more preferably 0.5 to 25%, based on the total solid content of the composition. % By mass, more preferably 3 to 20% by mass, particularly preferably 3 to 15% by mass.
- the acid generator is a specific acid generator represented by the above general formula (ZI-4) (when there are a plurality of types)
- the content is determined by the total solid content of the composition.
- 5 to 35% by mass is preferable
- 8 to 30% by mass is more preferable
- 9 to 30% by mass is further preferable
- 9 to 25% by mass is particularly preferable.
- the composition of the present invention may contain a hydrophobic resin (hereinafter also referred to as “hydrophobic resin (D)” or simply “resin (D)”).
- the hydrophobic resin (D) is preferably different from the resin P.
- the hydrophobic resin (D) is preferably designed to be unevenly distributed at the interface. However, unlike the surfactant, it is not always necessary to have a hydrophilic group in the molecule, and the polar / nonpolar substance is mixed uniformly. You don't have to contribute to Examples of the effects of adding the hydrophobic resin include control of the static / dynamic contact angle of the resist film surface with respect to water, improvement of immersion liquid followability, and suppression of outgas.
- the hydrophobic resin (D) is selected from any one of “fluorine atom”, “silicon atom”, and “CH 3 partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have the above, and it is more preferable to have two or more.
- the hydrophobic resin (D) contains a fluorine atom and / or a silicon atom
- the fluorine atom and / or silicon atom in the hydrophobic resin (D) may be contained in the main chain of the resin. , May be contained in the side chain.
- the hydrophobic resin (D) contains a fluorine atom
- it is a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.
- the alkyl group having a fluorine atom preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms
- a cycloalkyl group having a fluorine atom and an aryl group having a fluorine atom are a cycloalkyl group in which one hydrogen atom is substituted with a fluorine atom and an aryl group having a fluorine atom, respectively, and further a substituent other than a fluorine atom is substituted. You may have.
- alkyl group having a fluorine atom examples include groups represented by the following general formulas (F2) to (F4).
- the invention is not limited to this.
- R 57 to R 68 each independently represents a hydrogen atom, a fluorine atom or an alkyl group (straight or branched).
- R 57 to R 61 , at least one of R 62 to R 64 , and at least one of R 65 to R 68 are each independently a fluorine atom or at least one hydrogen atom is a fluorine atom. It represents a substituted alkyl group (preferably having 1 to 4 carbon atoms). All of R 57 to R 61 and R 65 to R 67 are preferably fluorine atoms.
- R 62 , R 63 and R 68 are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R 62 and R 63 may be connected to each other to form a ring.
- the hydrophobic resin (D) may contain a silicon atom.
- the partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
- Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in US2012 / 0251948A1 [0519].
- the hydrophobic resin (D) it is also preferred to include CH 3 partial structure side chain moiety.
- the CH 3 partial structure of the side chain portion in the hydrophobic resin (D) includes the CH 3 portion of an ethyl group, a propyl group, or the like. Includes structure.
- a methyl group directly bonded to the main chain of the hydrophobic resin (D) is caused by the influence of the main chain on the surface of the hydrophobic resin (D). Since the contribution to uneven distribution is small, it is not included in the CH 3 partial structure in the present invention.
- the hydrophobic resin (D) is a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M).
- R 11 to R 14 are CH 3 “as is”, the CH 3 is not included in the CH 3 partial structure of the side chain moiety in the present invention.
- CH 3 partial structure exists through some atoms from C-C backbone, and those falling under CH 3 partial structures in the present invention.
- R 11 is an ethyl group (CH 2 CH 3 )
- R 11 to R 14 each independently represents a side chain portion.
- R 11 to R 14 in the side chain portion include a hydrogen atom and a monovalent organic group.
- the monovalent organic group for R 11 to R 14 include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl.
- Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.
- the hydrophobic resin (D) is preferably a resin having a repeating unit having a CH 3 partial structure in the side chain portion, and as such a repeating unit, a repeating unit represented by the following general formula (II), and It is more preferable to have at least one repeating unit (x) among repeating units represented by the following general formula (III).
- X b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom
- R 2 has one or more CH 3 partial structure represents a stable organic radical to acid.
- the organic group that is stable to an acid is more specifically an organic group that does not have an acid-decomposable group (a group that decomposes by the action of an acid to generate a polar group such as a carboxy group). Is preferred.
- the alkyl group of Xb1 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.
- X b1 is preferably a hydrogen atom or a methyl group.
- R 2 include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH 3 partial structures.
- R 2 is preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH 3 partial structures.
- the acid-stable organic group having one or more CH 3 partial structures as R 2 preferably has 2 or more and 10 or less CH 3 partial structures, and more preferably 2 or more and 8 or less.
- Preferred specific examples of the repeating unit represented by the general formula (II) are shown below. The present invention is not limited to this.
- the repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.
- the repeating unit represented by formula (III) will be described in detail.
- X b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom
- R 3 represents an acid-stable organic group having one or more CH 3 partial structures
- n represents an integer of 1 to 5.
- the alkyl group of Xb2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom is preferable.
- X b2 is preferably a hydrogen atom. Since R 3 is an organic group that is stable against acid, more specifically, R 3 is preferably an organic group having no acid-decomposable group.
- R 3 includes an alkyl group having one or more CH 3 partial structures.
- the acid-stable organic group having one or more CH 3 partial structures as R 3 preferably has 1 or more and 10 or less CH 3 partial structures, more preferably 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less.
- n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.
- the repeating unit represented by the general formula (III) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.
- the repeating unit represented by the general formula (II) contains a CH 3 partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom
- the repeating unit represented by the general formula (II) contains a CH 3 partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom
- the content of at least one repeating unit (x) among the repeating units represented by the general formula (III) is preferably 90 mol% or more based on all repeating units of the hydrophobic resin (D). More preferably, it is 95 mol% or more. Content is 100 mol% or less normally with respect to all the repeating units of hydrophobic resin (D).
- the hydrophobic resin (D) comprises at least one repeating unit (x) among the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III). ),
- the surface free energy of the hydrophobic resin (D) increases.
- the hydrophobic resin (D) is less likely to be unevenly distributed on the surface of the resist film, and the static / dynamic contact angle of the resist film with respect to water can be reliably improved and the immersion liquid followability can be improved. it can.
- the hydrophobic resin (D) includes the following (x) to (z) regardless of whether (i) a fluorine atom and / or a silicon atom is included or (ii) a CH 3 partial structure is included in the side chain portion. ) May have at least one group selected from the group of (X) an acid group, (Y) a group having a lactone structure, an acid anhydride group, or an acid imide group, (Z) a group decomposable by the action of an acid
- Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) A methylene group etc. are mentioned.
- Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and
- the repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable.
- the repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.
- the content of the repeating unit having an acid group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 5%, based on all repeating units in the hydrophobic resin (D). 20 mol%.
- Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto.
- Rx represents a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
- the group having a lactone structure As the group having a lactone structure, the acid anhydride group, or the acid imide group (y), a group having a lactone structure is particularly preferable.
- the repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester.
- this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group.
- this repeating unit may be introduce
- Examples of the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the resin P.
- the content of the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 100 mol% based on all repeating units in the hydrophobic resin (D), The content is more preferably 3 to 98 mol%, further preferably 5 to 95 mol%.
- examples of the repeating unit having a group (z) that is decomposed by the action of an acid are the same as the repeating unit having an acid-decomposable group listed for the resin P.
- the repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom.
- the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol% with respect to all the repeating units in the resin (D). The amount is preferably 10 to 80 mol%, more preferably 20 to 60 mol%.
- the hydrophobic resin (D) may further have a repeating unit different from the above-described repeating unit.
- the repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on all repeating units contained in the hydrophobic resin (D). Further, the repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol% in all repeating units contained in the hydrophobic resin (D).
- hydrophobic resin (D) contains a CH 3 partial structure in the side chain portion
- a mode in which the hydrophobic resin (D) does not substantially contain a fluorine atom and a silicon atom is also preferable.
- hydrophobic resin (D) is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom.
- the standard polystyrene equivalent weight average molecular weight of the hydrophobic resin (D) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.
- the hydrophobic resin (D) may be used alone or in combination.
- the content of the hydrophobic resin (D) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition of the present invention.
- the residual monomer and oligomer components are preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass.
- the molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably in the range of 1 to 3.
- hydrophobic resin (D) various commercially available products can be used, and the hydrophobic resin (D) can be synthesized according to a conventional method (for example, radical polymerization).
- Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).
- R 200 , R 201 and R 202 may be the same or different and are a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (having a carbon number). 6-20), wherein R 201 and R 202 may combine with each other to form a ring.
- R 203 , R 204 , R 205 and R 206 may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
- the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
- the alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.
- Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.
- Specific examples of preferred compounds include the compounds exemplified in paragraph ⁇ 0379> of US Patent Application Publication No. 2012/0219913.
- Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.
- These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more types.
- the composition of the present invention may or may not contain a basic compound.
- the content of the basic compound is usually 0.001 to 10 mass based on the solid content of the composition. %, Preferably 0.01 to 5% by mass.
- the use ratio of the acid generator and the basic compound in the composition is preferably 2.5 to 300, more preferably 5.0 to 200, and still more preferably molar ratio (acid generator / basic compound). 7.0-150.
- a low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid is an amine derivative having a group on the nitrogen atom that is leaving by the action of an acid. It is preferable that As the group capable of leaving by the action of an acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, and a hemiaminal ether group are preferable, and a carbamate group and a hemiaminal ether group are particularly preferable. .
- the molecular weight of the compound (C) is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.
- Compound (C) may have a carbamate group having a protecting group on the nitrogen atom.
- the protecting group constituting the carbamate group can be represented by the following general formula (d-1).
- R b each independently represents a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group. (Preferably having 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms).
- R b may be connected to each other to form a ring.
- the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R b are substituted with a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, and an oxo group, an alkoxy group, and a halogen atom. May be. The same applies to the alkoxyalkyl group represented by Rb.
- R b is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.
- Examples of the ring formed by connecting two R b to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.
- Examples of the specific structure of the group represented by the general formula (d-1) include the structure disclosed in paragraph ⁇ 0466> of US Patent Application Publication No. 2012/0135348. It is not limited.
- the compound (C) has a structure represented by the following general formula (6).
- R a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.
- l represents 2 R a may be the same or different, and two R a may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula.
- the heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.
- R b has the same meaning as R b in formula (d-1), and preferred examples are also the same.
- l represents an integer of 0 to 2
- the alkyl group, cycloalkyl group, aryl group and aralkyl group as R a are the groups in which the alkyl group, cycloalkyl group, aryl group and aralkyl group as R b may be substituted. It may be substituted with a group similar to the group described above.
- R b includes the same groups as the specific examples described above.
- Specific examples of the particularly preferable compound (C) in the present invention include, but are not limited to, compounds disclosed in paragraph ⁇ 0475> of US Patent Application Publication No. 2012/0135348.
- the compound represented by the general formula (6) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.
- the low molecular compound (C) having a group capable of leaving by the action of an acid on the nitrogen atom can be used singly or in combination of two or more.
- the content of the compound (C) in the composition of the present invention is preferably 0.001 to 20% by mass, more preferably 0.001 to 10% by mass, further based on the total solid content of the composition.
- the content is 0.01 to 5% by mass.
- an onium salt that becomes a weak acid relative to the acid generator can be used as an acid diffusion control agent.
- an acid generator and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated from the acid generator are mixed and used, the acid generated from the acid generator by irradiation with actinic rays or radiation When it collides with an onium salt having an unreacted weak acid anion, a weak acid is released by salt exchange to produce an onium salt having a strong acid anion.
- the strong acid is exchanged with a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.
- the onium salt that is a weak acid relative to the acid generator is preferably a compound represented by the following general formulas (d1-1) to (d1-3).
- R 51 represents a hydrocarbon group which may have a substituent
- Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, a carbon adjacent to S).
- R 52 is an organic group
- Y 3 is a linear, branched or cyclic alkylene group or an arylene group
- Rf is a fluorine atom.
- Each of the M + is independently a sulfonium or iodonium cation.
- sulfonium cation or iodonium cation represented by M + include a sulfonium cation exemplified by the general formula (ZI) and an iodonium cation exemplified by the general formula (ZII).
- Preferable examples of the anion moiety of the compound represented by the general formula (d1-1) include the structures exemplified in paragraph [0198] of JP2012-242799A.
- Preferable examples of the anion moiety of the compound represented by the general formula (d1-2) include the structures exemplified in paragraph [0201] of JP2012-242799A.
- Preferable examples of the anion moiety of the compound represented by the general formula (d1-3) include the structures exemplified in paragraphs [0209] and [0210] of JP2012-242799A.
- the onium salt that is a weak acid relative to the acid generator is a compound (C) having a cation moiety and an anion moiety in the same molecule, and the cation moiety and the anion moiety being linked by a covalent bond (Hereinafter also referred to as “compound (CA)”).
- the compound (CA) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).
- R 1 , R 2 and R 3 represent a substituent having 1 or more carbon atoms.
- L 1 represents a divalent linking group or a single bond linking the cation moiety and the anion moiety.
- -X - it is, -COO -, -SO 3 - represents an anion portion selected from -R 4 -, -SO 2 -, -N.
- R 4 is a group having a carbonyl group: —C ( ⁇ O) —, a sulfonyl group: —S ( ⁇ O) 2 —, and a sulfinyl group: —S ( ⁇ O) — at the site of connection with the adjacent N atom.
- R 1 , R 2 , R 3 , R 4 and L 1 may be bonded to each other to form a ring structure.
- R 1 to R 3 may be combined to form a double bond with the N atom.
- Examples of the substituent having 1 or more carbon atoms in R 1 to R 3 include alkyl group, cycloalkyl group, aryl group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, cycloalkylamino A carbonyl group, an arylaminocarbonyl group, etc. are mentioned. Preferably, they are an alkyl group, a cycloalkyl group, and an aryl group.
- L 1 as the divalent linking group is a linear or branched alkylene group, cycloalkylene group, arylene group, carbonyl group, ether bond, ester bond, amide bond, urethane bond, urea bond, and two types thereof. Examples include groups formed by combining the above. L 1 is more preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.
- Preferable examples of the compound represented by the general formula (C-1) include paragraphs [0037] to [0039] of JP2013-6827A and paragraphs [0027] to [0029] of JP2013-8020A. ] Can be mentioned.
- Preferable examples of the compound represented by the general formula (C-2) include compounds exemplified in paragraphs [0012] to [0013] of JP2012-189977A.
- Preferable examples of the compound represented by the general formula (C-3) include the compounds exemplified in paragraphs [0029] to [0031] of JP 2012-252124 A.
- the content of the onium salt that is a weak acid relative to the acid generator is preferably 0.5 to 10.0% by mass, and preferably 0.5 to 8.0% by mass based on the solid content of the composition. % Is more preferable, and 1.0 to 8.0% by mass is even more preferable.
- Solvents that can be used in preparing the composition include, for example, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 4 carbon atoms). 10), an organic solvent such as a monoketone compound (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate and the like. Specific examples of these solvents include those described in US Patent Application Publication No. 2008/0187860 ⁇ 0441> to ⁇ 0455>.
- the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group the above-mentioned exemplary compounds can be selected as appropriate.
- the solvent containing a hydroxyl group alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether ( PGME, also known as 1-methoxy-2-propanol), methyl 2-hydroxyisobutyrate, and ethyl lactate are more preferred.
- alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether Acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone, butyl acetate are particularly preferred, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2 -Heptanone is most preferred.
- PGMEA propylene glycol monomethyl ether Acetate
- ethyl ethoxypropionate 2-heptanone
- ⁇ -butyrolactone cyclohexanone
- the mixing ratio (mass ratio) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. is there.
- a mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.
- the solvent preferably contains propylene glycol monomethyl ether acetate, more preferably a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.
- composition of the present invention may or may not further contain a surfactant. When it is contained, it contains a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based surfactant). Surfactants, surfactants having both fluorine and silicon atoms) are preferred.
- composition of the present invention contains a surfactant
- a surfactant when using an exposure light source of 250 nm or less, particularly 220 nm or less, it is possible to provide a resist pattern with less adhesion and development defects with good sensitivity and resolution.
- the fluorine-based and / or silicon-based surfactant include surfactants described in paragraph ⁇ 0276> of US Patent Application Publication No. 2008/0248425.
- surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph ⁇ 0280> of US Patent Application Publication No. 2008/0248425 can also be used.
- the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1%, based on the total solid content of the composition. % By mass.
- the addition amount of the surfactant 10 ppm or less with respect to the total amount of the composition (excluding the solvent) the surface unevenness of the hydrophobic resin is increased, thereby making the resist film surface more hydrophobic. It is possible to improve water followability at the time of immersion exposure.
- composition of the present invention may or may not contain an onium carboxylate.
- carboxylic acid onium salts include those described in US Patent Application Publication No. 2008/0187860 ⁇ 0605> to ⁇ 0606>. These carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.
- the content thereof is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, based on the total solid content of the composition. More preferably, it is 1 to 7% by mass.
- the composition of the present invention may further include an acid proliferator, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, and a compound that promotes solubility in a developer ( For example, a phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound) can be contained.
- Such phenol compounds having a molecular weight of 1000 or less are described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, and the like. It can be easily synthesized by those skilled in the art with reference to the method described.
- alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples include, but are not limited to, dicarboxylic acids.
- the composition of the present invention is preferably a resist film having a thickness of 80 nm or less from the viewpoint of improving resolution.
- a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.
- the solid content concentration of the composition in the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0 to 5.3% by mass.
- the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, which suppresses aggregation of the material in the resist solution, particularly the photoacid generator. As a result, it is considered that a uniform resist film was formed.
- the solid content concentration is a mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the composition.
- the above components are dissolved in a predetermined organic solvent, preferably the above mixed solvent, filtered, and then applied onto a predetermined support (substrate).
- the pore size of the filter used for filter filtration is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and still more preferably 0.03 ⁇ m or less made of polytetrafluoroethylene, polyethylene, or nylon.
- filter filtration for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel.
- the composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and behind filter filtration.
- the composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition whose properties change upon irradiation with actinic rays or radiation. More specifically, the present invention relates to semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, production of imprint mold structures, and other photofabrication processes, lithographic printing plates, acid-curing properties. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used in the composition.
- the pattern forming method of the present invention comprises: (I) forming a film (actinic ray-sensitive or radiation-sensitive resin composition film, composition film, resist film) on a substrate with the composition of the present invention; (Ii) a step of irradiating (exposing) active light or radiation to the film (exposure step), and (iii) a step of developing the film irradiated with the active light or radiation using a developer containing an organic solvent. (Development process), At least.
- the exposure in the step (ii) may be immersion exposure.
- the pattern forming method of the present invention preferably includes (ii) a heating step after the (ii) exposure step.
- the pattern forming method of the present invention may include (ii) an exposure step a plurality of times.
- the pattern forming method of the present invention may include (iv) a heating step a plurality of times.
- the resist film in the present invention is formed from the above-described composition of the present invention, and more specifically, is preferably a film formed by applying the composition on a substrate.
- the step of forming a film of the composition on the substrate, the step of exposing the film, and the developing step can be performed by generally known methods.
- a substrate on which a film is formed is not particularly limited, and is generally used in a manufacturing process of a semiconductor such as an IC, a manufacturing process of a circuit board such as a liquid crystal or a thermal head; a lithography process of other photofabrication;
- substrates include inorganic substrates such as silicon, SiO 2 , and SiN; coated inorganic substrates such as SOG (Spin On Glass); and the like.
- an antireflection film may be formed between the resist film and the substrate.
- the antireflection film a known organic or inorganic antireflection film can be appropriately used.
- PB preheating step
- PEB post-exposure heating step
- the heating temperature is preferably 70 to 130 ° C., more preferably 80 to 120 ° C. for both PB and PEB.
- the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds. Heating can be performed by means provided in a normal exposure machine and developing machine, and may be performed using a hot plate or the like. The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.
- Infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, an electron beam, etc. can be mentioned, Preferably it is 250 nm or less.
- KrF excimer laser 248 nm
- ArF excimer laser (193 nm)
- F 2 excimer laser 157 nm
- X-ray EUV
- EUV 13 nm
- electron beam etc.
- KrF excimer laser, ArF excimer laser, EUV or electron beam are preferable, and ArF excimer laser is more preferable.
- the immersion exposure method can be applied in the step of performing exposure in the present invention.
- the immersion exposure method can be combined with a super-resolution technique such as a phase shift method or a modified illumination method.
- the immersion exposure can be performed, for example, according to the method described in paragraphs ⁇ 0594> to ⁇ 0601> of JP2013-242397A.
- the receding contact angle of the resist film formed using the composition of the present invention is too small, it cannot be suitably used for exposure through an immersion medium, and water residue defects can be reduced. The effect of can not be fully demonstrated.
- the hydrophobic resin (D) in the composition.
- an immersion liquid hardly soluble film hereinafter also referred to as “top coat” formed of the above-described hydrophobic resin (D) may be provided on the upper layer of the resist film. The necessary functions for the top coat are appropriate application to the upper layer of the resist film and poor immersion liquid solubility.
- the top coat is not mixed with the composition film and can be uniformly applied to the upper layer of the composition film.
- the topcoat is not particularly limited, and a conventionally known topcoat can be formed by a conventionally known method. For example, based on the description in paragraphs ⁇ 0072> to ⁇ 0082> of JP-A-2014-059543 Can be formed.
- a developer containing an organic solvent is used in the development step described later, it is preferable to form a top coat containing a basic compound described in JP2013-61648A on the resist film. Further, even when the exposure is performed by a method other than the immersion exposure method, a top coat may be formed on the resist film.
- the immersion liquid needs to move on the wafer following the movement of the exposure head scanning the wafer at high speed to form an exposure pattern, so the resist film in a dynamic state
- the contact angle of the immersion liquid with respect to is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.
- a developer containing an organic solvent hereinafter also referred to as “organic developer”.
- organic developer polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.
- ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, and isophorone.
- ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, Diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate Butyl butanoate, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, butyl propionate, propylene carbonate, etc.
- the alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol; glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl Ether, triethylene glycol monoethyl ether, methoxymethylbuta Glycol ether solvents such Lumpur; and the like.
- Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
- Examples of amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like.
- Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane;
- the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water.
- the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture. That is, the content of the organic solvent with respect to the organic developer is preferably 90% by mass to 100% by mass and more preferably 95% by mass to 100% by mass with respect to the total amount of the developer.
- the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .
- the vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
- the vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
- the surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.
- fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in US Pat. Nos.
- the surfactant content is usually from 0.001 to 5 mass%, preferably from 0.005 to 2 mass%, more preferably from 0.01 to 0.5 mass%, based on the total amount of the developer.
- the organic developer may contain a basic compound.
- Specific examples and preferred examples of the basic compound that can be contained in the organic developer are the same as those in the basic compound that can be contained in the composition of the present invention.
- a developing method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc.
- the preferred range of the discharge pressure of the discharged developer and the method for adjusting the discharge pressure of the developer are not particularly limited. For example, paragraphs ⁇ 0631> to ⁇ 063 of JP 2013-242397 A 0636> can be used.
- a step of developing using a developer containing an organic solvent (organic solvent developing step) and a step of developing using an alkaline aqueous solution (alkali developing step) are used in combination. Also good. Thereby, a finer pattern can be formed.
- organic solvent developing step organic solvent developing step
- alkali developing step alkaline aqueous solution
- a portion with low exposure intensity is removed by the organic solvent development step, but a portion with high exposure strength is also removed by further performing the alkali development step.
- a pattern can be formed without dissolving only the intermediate exposure intensity region, so that a finer pattern than usual can be formed (Japanese Patent Laid-Open No. 2008-292975 ⁇ 0077). The same mechanism as>.
- the rinsing solution used in the rinsing step after the step of developing with a developer containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used.
- a rinsing liquid a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents should be used. Is preferred. Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent.
- a step of washing with a rinsing liquid containing various organic solvents is performed, more preferably a step of washing with a rinsing liquid containing an alcohol solvent or an ester solvent, and particularly preferably a monohydric alcohol.
- the washing step is performed using a rinse solution containing, and most preferably, the washing step is performed using a rinse solution containing a monohydric alcohol having 5 or more carbon atoms.
- examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols. Specific examples include 1-butanol, 2-butanol, and 3-methyl-1-butanol. Tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2 -Octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms are 1-hexanol, 2-hexanol, 4-methyl- Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. Can.
- a hydrocarbon compound having 6 to 30 carbon atoms is preferable, a hydrocarbon compound having 8 to 30 carbon atoms is more preferable, and a hydrocarbon compound having 8 to 30 carbon atoms is more preferable.
- a hydrocarbon compound having 10 to 30 carbon atoms is particularly preferred.
- pattern collapse is suppressed by using the rinse liquid containing a decane and / or undecane.
- a glycol ether solvent may be used in addition to the ester solvent (one or more).
- ester solvent preferably butyl acetate
- glycol ether solvent preferably propylene glycol monomethyl ether (PGME)
- a plurality of each component may be mixed, or may be used by mixing with an organic solvent other than the above.
- the water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.
- the vapor pressure of the rinsing solution used after the step of developing with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable.
- the wafer that has been developed using the developer containing the organic solvent is cleaned using the rinse solution containing the organic solvent.
- the cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), etc. can be applied. Among these, a cleaning process is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm.
- the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking.
- the heating step after the rinsing step is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.
- Various materials used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and the pattern forming method of the present invention preferably does not contain impurities such as metals.
- the content of impurities contained in these materials is preferably 1 ppm or less, more preferably 100 ppt or less, still more preferably 10 ppt or less, and particularly preferably (not more than the detection limit of the measuring device). Examples of a method for removing impurities such as metals from the various materials include filtration using a filter.
- the pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less.
- the filter material is preferably a polytetrafluoroethylene, polyethylene, or nylon filter.
- a filter that has been washed in advance with an organic solvent may be used.
- a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
- a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials.
- the inside of the apparatus may be lined with Teflon (registered trademark), and distillation may be performed under a condition in which contamination is suppressed as much as possible.
- the preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.
- impurities may be removed with an adsorbent, or a combination of filter filtration and adsorbent may be used.
- the adsorbent known adsorbents can be used.
- inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
- a method for improving the surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention.
- a method for improving the surface roughness of the pattern for example, a method of treating a resist pattern with a plasma of a hydrogen-containing gas disclosed in International Publication No. 2014/002808 can be mentioned.
- JP 2004-235468 A, US Patent Application Publication No. 2010/0020297, JP 2009-19969 A, Proc. of SPIE Vol. 8328 83280N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement” may be applied.
- the pattern forming method of the present invention can also be used for guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Pages 4815-4823). Further, the resist pattern formed by the above method can be used as a core material (core) of a spacer process disclosed in, for example, JP-A-3-270227 and JP-A-2013-164509.
- DSA Directed Self-Assembly
- the resist pattern formed by the above method can be used as a core material (core) of a spacer process disclosed in, for example, JP-A-3-270227 and JP-A-2013-164509.
- the present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention.
- An electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electric / electronic device (for example, home appliances, OA-related devices, media-related devices, optical devices, and communication devices). It is.
- the same operations as in Synthesis Example 1 were performed to synthesize resins B-2 to B-12 described later.
- ⁇ Preparation of resist composition> The components shown in Table 1 below were dissolved in the solvent shown in the same table in the blending amounts (unit: parts by mass) shown in the same table. Each solution was prepared to be a solution having a solid content concentration of 4% by mass. Furthermore, the resist composition (resist compositions of Examples and Comparative Examples) was prepared by filtering the solution through a polyethylene filter having a pore size of 0.05 ⁇ m. In Table 1 below, for the solvents, the numerical values in parentheses represent mass ratios.
- the resulting resist film was exposed through an ArF immersion exposure machine (XT1700i; manufactured by ASML, NA 1.20, Annular, outer sigma 0.80, inner sigma 0.64) through a mask having a pitch of 550 nm and a light shielding part of 90 nm. .
- the exposed resist film was baked at 100 ° C. for 60 seconds (Post Exposure Bake; PEB) and then developed using an organic developer (butyl acetate) to form a contact hole pattern having a hole diameter of 45 nm. .
- PEB Post Exposure Bake
- an organic developer butyl acetate
- the hole diameter (CD) of each pattern obtained was measured with a line width measurement scanning electron microscope SEM (S-9380; manufactured by Hitachi, Ltd.), and the CD change was observed.
- a focus fluctuation range allowing 45 nm ⁇ 10% with respect to the maximum value in the observed CD, that is, a focus tolerance (DOF) was calculated.
- Table 1 shows the results. The larger the value of DOF, the better the performance because the CD variation with respect to the focus shift is smaller.
- a topcoat composition containing 2.5% by mass of the following resin, 0.5% by mass of the amine compound shown below, and 97% by mass of 4-methyl-2-pentanol solvent was used. Then, a top coat layer having a thickness of 100 nm was provided on the resist film.
- An organic antireflection film-forming composition ARC29SR (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form an organic antireflection film having a thickness of 95 nm.
- the resist composition obtained on the organic antireflection film was applied and baked (PB: Prebake) at 100 ° C. for 60 seconds. As a result, a resist film having a thickness of 100 nm was obtained.
- the obtained resist film was used with an ArF immersion exposure machine (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection) 1: Exposure was through a 6% halftone mask with a one line and space pattern. Ultra pure water was used as the immersion liquid. Thereafter, the exposed resist film was heated at 100 ° C. for 60 seconds (PEB: Post Exposure Bake). Subsequently, it was developed by paddling with butyl acetate for 30 seconds, and rinsed by padding with a rinsing solution [methyl isobutyl carbinol (MIBC)] for 30 seconds.
- MIBC methyl isobutyl carbinol
- Example 12 a top coat layer was provided in the same manner as in the DOF evaluation.
- the composition ratio of the repeating unit is a molar ratio.
- the weight average molecular weight (Mw) and dispersity (Mw / Mn) are shown in Table 2 below. These were obtained by the same method as that for the resin B-1.
- Table 3 shows the composition ratio (molar ratio; corresponding in order from the left), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit for each hydrophobic resin. These were obtained by the same method as that for the resin B-1.
- Comparative Example 1 is an example using Resin B-13 having no repeating unit Q2
- Comparative Example 2 is an example using Resin B-14 having a repeating unit Q2 content of less than 20 mol%.
- Comparative Example 3 is an example using Resin B-15 that does not have the repeating unit Q1.
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Abstract
Description
より詳細には、本発明は、IC等の半導体製造工程、液晶及びサーマルヘッド等の回路基板の製造、並びにその他のフォトファブリケーションのリソグラフィー工程に好適なパターン形成方法、及びそれに用いられる感活性光線性又は感放射線性樹脂組成物(レジスト組成物)に関する。また、本発明は、上記パターン形成方法を含む電子デバイスの製造方法にも関する。
例えば、特許文献1および2には、ラクトン環が主鎖に直結した繰り返し単位を有する樹脂を含有するレジスト組成物が開示されている。
[1](i)感活性光線性又は感放射線性樹脂組成物によって基板上に感活性光線性又は感放射線性樹脂組成物膜を形成する工程、(ii)上記膜に活性光線又は放射線を照射する工程、及び、(iii)上記活性光線又は放射線が照射された膜を、有機溶剤を含有する現像液を用いて現像する工程、を少なくとも有するパターン形成方法であって、上記感活性光線性又は感放射線性樹脂組成物が、樹脂Pと、活性光線又は放射線の照射により酸を発生する化合物とを含有し、上記樹脂Pが、後述する一般式(q1)で表される繰り返し単位Q1、及び、後述する一般式(q2)で表される繰り返し単位Q2を有し、上記樹脂Pの全繰り返し単位に対する、上記繰り返し単位Q2の含有量が、20モル%以上である、パターン形成方法。
[2]上記一般式(q2)中、R9が、炭素数3~14の多環式シクロアルキル基を表す、上記[1]に記載のパターン形成方法。
[3]上記樹脂Pが、更に、上記繰り返し単位Q1とは異なるラクトン構造を有する繰り返し単位を有する、上記[1]又は[2]に記載のパターン形成方法。
[4]上記樹脂Pの全繰り返し単位に対する、上記繰り返し単位Q2の含有量が、40モル%以上である、上記[1]~[3]のいずれかに記載のパターン形成方法。
[5]上記樹脂Pの全繰り返し単位に対する、上記繰り返し単位Q2の含有量が、50モル%以上である、上記[4]に記載のパターン形成方法。
[6]上記樹脂Pが、上記繰り返し単位Q1と、上記繰り返し単位Q2と、上記繰り返し単位Q1とは異なるラクトン構造を有する繰り返し単位とのみからなる樹脂である、上記[1]~[5]のいずれかに記載のパターン形成方法。
[7]上記[1]~[6]のいずれかに記載のパターン形成方法を含む、電子デバイスの製造方法。
[8]樹脂Pと、活性光線又は放射線の照射により酸を発生する化合物とを含有し、上記樹脂Pが、後述する一般式(q1)で表される繰り返し単位Q1、及び、後述する一般式(q2)で表される繰り返し単位Q2を有し、上記樹脂Pの全繰り返し単位に対する、上記繰り返し単位Q2の含有量が、20モル%以上である、感活性光線性又は感放射線性樹脂組成物。
[9]上記一般式(q2)中、R9が、炭素数3~14の多環式シクロアルキル基を表す、上記[8]に記載の感活性光線性又は感放射線性樹脂組成物。
[10]上記樹脂Pが、更に、上記繰り返し単位Q1とは異なるラクトン構造を有する繰り返し単位を有する、上記[8]又は[9]に記載の感活性光線性又は感放射線性樹脂組成物。
[11]上記樹脂Pの全繰り返し単位に対する、上記繰り返し単位Q2の含有量が、40モル%以上である、上記[8]~[10]のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
[12]上記樹脂Pの全繰り返し単位に対する、上記繰り返し単位Q2の含有量が、50モル%以上である、上記[11]に記載の感活性光線性又は感放射線性樹脂組成物。
[13]上記樹脂Pが、上記繰り返し単位Q1と、上記繰り返し単位Q2と、上記繰り返し単位Q1とは異なるラクトン構造を有する繰り返し単位とのみからなる樹脂である、上記[8]~[12]のいずれかに記載の感活性光線性又は感放射線性樹脂組成物。
本明細書における基及び原子団の表記において、置換又は無置換を明示していない場合は、置換基を有さないものと置換基を有するものの双方が含まれるものとする。例えば、置換又は無置換を明示していない「アルキル基」は、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含することとする。
本発明において「活性光線」又は「放射線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、電子線、イオンビーム等の粒子線等を意味する。また、本発明において「光」とは、活性光線又は放射線を意味する。
また、本明細書中における「露光」とは、特に断らない限り、水銀灯、エキシマレーザーに代表される遠紫外線、X線、極紫外線(EUV光)などによる露光のみならず、電子線、イオンビーム等の粒子線による描画も含まれるものとする。
本明細書では、「(メタ)アクリレート」とは、「アクリレート及びメタクリレートの少なくとも1種」を意味する。また、「(メタ)アクリル酸」とは、「アクリル酸及びメタクリル酸の少なくとも1種」を意味する。
本明細書において「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
このような樹脂Pを用いることにより、本発明においては、大きなフォーカス許容度(Depth of Focus:DOF)が得られる。
その理由は、明らかではないが、以下のように推測される。
一方、後述する一般式(q2)で表される繰り返し単位Q2においては、酸の作用によって、酸素原子と第4級炭素原子との間の共有結合が切断され、第4級炭素原子を含む保護基が脱離する。このとき、脱離した保護基は、すぐには揮散等せずに、しばらくはレジスト膜中に残存し、酸の拡散を助ける役割を果たすと考えられる。本発明においては、繰り返し単位Q2の含有量が20モル%以上と多いため、脱離する保護基の量も多くなり、酸の拡散がより良好になると考えられる。
このとき、後述する一般式(q2)で表される繰り返し単位Q2の保護基においては、第4級炭素原子に結合する炭素原子(後述する一般式(q2)中のR7~R9)どうしが環構造を形成していない。このような保護基は、第4級炭素原子に結合する炭素原子どうしが環構造を形成している保護基と比べて、酸との相互作用が良好となるため、より酸の拡散性が良化すると考えられる。
加えて、上述したように、後述する一般式(q1)で表される繰り返し単位Q1のガラス転移温度の低下量が大きいため、酸が移動しやすく、脱離した保護基による酸の拡散性がより向上すると考えられる。
上記のようにして、酸の拡散性が良好となる結果、大きなDOFが得られると考えられる。
本発明の感活性光線性又は感放射線性樹脂組成物(以下、「本発明の組成物」又は「本発明のレジスト組成物」とも称する。)は、樹脂Pと、活性光線又は放射線の照射により酸を発生する化合物とを含有する。
ここで、上記樹脂Pは、後述する一般式(q1)で表される繰り返し単位Q1、及び、後述する一般式(q2)で表される繰り返し単位Q2を有し、上記樹脂Pの全繰り返し単位に対する、上記繰り返し単位Q2の含有量が、20モル%以上である。
このような本発明の組成物は、ネガ型の現像(露光部がパターンとして残り、未露光部が除去される現像)に用いられる。即ち、有機溶剤を含む現像液を用いて現像を行う。
樹脂Pは、少なくとも、後述する一般式(q1)で表される繰り返し単位Q1、及び、後述する一般式(q2)で表される繰り返し単位Q2を有する。
繰り返し単位Q1は、下記一般式(q1)で表される繰り返し単位である。
一般式(q1)中のR1が表す炭素数1~20の有機基としては、例えば、炭素数1~20の鎖状炭化水素基、炭素数3~20の脂環式炭化水素基、炭素数6~20の芳香族炭化水素基、環員数3~10の複素環基、エポキシ基、シアノ基、カルボキシ基、-R’-Q-R’’で表される基等が挙げられる。但し、R’は、単結合又は炭素数1~20の炭化水素基である。R’’は、置換されていてもよい炭素数1~20の炭化水素基又は環員数3~10の複素環基である。Qは、-O-、-CO-、-NH-、-SO2-、-SO-又はこれらを組み合わせてなる基である。上記鎖状炭化水素基、脂環式炭化水素基及び芳香族炭化水素基が有する水素原子の一部又は全部は、例えば、フッ素原子などのハロゲン原子;シアノ基、カルボキシ基、ヒドロキシ基、チオール基、トリアルキルシリル基などの置換基;等で置換されていてもよい。
上記炭素数3~20の脂環式炭化水素基としては、例えば、シクロプロピル基、シクロブチル基、シクロへキシル基、シクロオクチル基、シクロデシル基などの単環の脂環式炭化水素基;ノルボルニル基、アダマンチル基などの多環の脂環式炭化水素基;等が挙げられる。
上記炭素数6~20の芳香族炭化水素基としては、例えば、フェニル基、ナフチル基等が挙げられる。
上記環員数3~10の複素環基を構成する複素環としては、例えば、ラクトン環、環状カーボネート、スルトン環、フラン環、チオフェン環、ベンゾフラン環、ベンゾチオフェン環、ジベンゾフラン環、ジベンゾチオフェン環、ピリジン環等が挙げられる。これらのうち、ラクトン環、環状カーボネート、スルトン環が好ましく、ラクトン環がより好ましい。
上記-R’-Q-R’’におけるR’及びR’’で表される炭素数1~20の炭化水素基としては、例えば、炭素数1~20の鎖状炭化水素基、炭素数3~20の脂環式炭化水素基、炭素数6~20の芳香族炭化水素基等が挙げられる。それぞれについては、上記R1で表される炭素数1~20の有機基として例示した基と同様の基を挙げることができる。また、R’’で表される環員数3~10の複素環基については、上記R1で表される環員数3~10の複素環基の説明を適用できる。
一般式(q1)中のR2~R5が表す炭素数1~20の有機基の具体例および好適な態様は、上述した一般式(q1)中のR1が表す炭素数1~20の有機基と同じである。
R2とR3、及びR4とR5が、互いに結合して、これらが結合している炭素原子と共にそれぞれ形成していてもよい環員数3~10の環構造としては、例えば、シクロプロパン、シクロペンタン、シクロヘキサン、ノルボルナン、アダマンタンなどの脂環を有する脂環式構造;ヘテロ原子を含む環を有する複素環構造;等が挙げられる。
ヘテロ原子を含む環を有する複素環構造としては、例えば、環状エーテル、ラクトン環、又はスルトン環を有する複素環構造が挙げられ、その他の具体例としては、テトラヒドロフラン、テトラヒドロピラン、γ-ブチロラクトン、δ-バレロラクトン、オキソラン、ジオキサンなどの酸素原子を含む環を有する複素環構造;テトラヒドロチオフェン、テトラヒドロチオピラン、テトラヒドロチオフェン-1,1-ジオキシド、テトラヒドロチオピラン-1,1-ジオキシド、シクロペンタンチオン、シクロヘキサンチオンなどの硫黄原子を含む環を有する複素環構造;ピペリジンなどの窒素原子を含む環を有する複素環構造;等が挙げられる。
これらのうち、シクロペンタン、シクロヘキサン、又はアダマンタンを有する脂環式構造、及び、環状エーテル、ラクトン環、又はスルトン環を有する複素環構造が好ましい。
ここで、R2とR3、及びR4とR5が、互いに結合して、これらが結合している炭素原子と共にそれぞれ形成していてもよい環員数3~10の環構造における「環構造」とは、環を含む構造をいい、環のみから形成されていてもよいし、環と置換基等の他の基とから形成されていてもよい。なお、R2とR3、及びR4とR5が、互いに結合している場合における上記結合は、化学反応を経由した結合に限定されない。
なお、一般式(q1)中、aが2以上の場合、複数のR2及びR3はそれぞれ同一であってもよく、異なっていてもよい。
R2及びR3としては、水素原子、炭素数1~20の鎖状炭化水素基が好ましく、水素原子がより好ましい。
上記樹脂Pの全繰り返し単位に対する、一般式(q1)で表される繰り返し単位Q1の含有量は特に制限されないが、5~60モル%が好ましく、5~50モル%がより好ましく、10~40モル%が更に好ましい。
繰り返し単位Q2は、下記一般式(q2)で表される繰り返し単位であり、通常、酸の作用によって分解し、酸素原子と第4級炭素原子との間の共有結合が切断され、カルボキシ基を生じる。
ただし、一般式(q2)中において、R7~R9は、そのうちの2つが互いに結合して環構造を形成しない。
一般式(q2)中のR6が表す炭素数1~20の有機基の具体例および好適な態様は、上述した一般式(q1)中のR1が表す炭素数1~20の有機基と同じである。
一般式(q2)中、R6としては、水素原子、炭素数1~20の鎖状炭化水素基が好ましく、水素原子、メチル基がより好ましい。
一般式(q2)中のR7及びR8が表す炭素数1~10の分岐構造を含んでよい鎖状のアルキル基としては、例えば、メチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基、iso-ブチル基、tert-ブチル基、n-ヘキシル基、n-オクチル基などが挙げられ、なかでも、メチル基、エチル基、n-プロピル基、iso-プロピル基が好ましい。
一般式(q2)中のR9が表す炭素数1~10の分岐構造を含んでよいアルキル基としては、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、イソブチル基、tert-ブチル基、n-ヘキシル基、n-オクチル基などが挙げられ、なかでも、メチル基、エチル基、n-プロピル基、イソプロピル基が好ましい。
一般式(q2)中のR9が表す炭素数3~14の単環式又は多環式のシクロアルキル基としては、例えば、シクロペンチル基、シクロヘキシル基などの炭素数3~14の単環式のシクロアルキル基;ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、アダマンチル基などの炭素数3~14の多環式のシクロアルキル基;等が挙げられ、なかでも、炭素数3~14の多環式のシクロアルキル基が好ましく、アダマンチル基がより好ましい。
上記樹脂Pの全繰り返し単位に対する、一般式(q1)で表される繰り返し単位Q1、および、一般式(q2)で表される繰り返し単位Q2の合計含有量は、25モル%~100モル%であることが好ましく、30モル%~100モル%であることがより好ましく、40モル%~100モル%であることがさらに好ましく、50モル%~100モル%であることが特に好ましい。
上記樹脂Pは、更に、繰り返し単位Q3を有していてもよい。
繰り返し単位Q3は、下記一般式(q3)で表される繰り返し単位であって、かつ、上述した一般式(q2)で表される繰り返し単位Q2とは異なる繰り返し単位である。繰り返し単位Q3は、通常、酸の作用によって分解し、酸素原子と第4級炭素原子との間の共有結合が切断され、カルボキシ基を生じる。
一般式(q3)中のR62の具体例および好適な態様は、上述した一般式(q2)中のR6と同じである。
一般式(q3)中のR72~R92の具体例および好適な態様は、R72~R92のうち2つが互いに結合して環構造を形成しないこと以外は、それぞれ、上述した一般式(q2)中のR7~R9と同じである。
一般式(q32)中、R62は、一般式(q3)中のR62と同義である。
また、一般式(q32)中、R789は、環構造を表す。R789が表す環構造としては、炭素数3~20の環構造が好ましく、炭素数3~14の環構造がより好ましく、例えば、ノルボルニル基、アダマンチル基などの多環の環構造が挙げられる。
上記樹脂Pが繰り返し単位Q3を有する場合、上記樹脂Pの全繰り返し単位に対する繰り返し単位Q3の含有量は、50モル%以下が好ましく、40モル%以下がより好ましい。下限は特に限定されないが、例えば、10モル%以上である。
樹脂Pは、更に、上述した繰り返し単位Q1とは異なるラクトン構造を有する繰り返し単位(以下、単に「ラクトン構造を有する繰り返し単位」または「繰り返し単位(a)」ともいう。)を有することが好ましい。
繰り返し単位(a)は、1種単独で用いてもよく、2種以上を併用していてもよいが、1種単独で用いることが好ましい。
上記樹脂Pの全繰り返し単位に対する、上記繰り返し単位(a)の含有量は、繰り返し単位(a)が有する構造にもよるが、例えば、3~80モル%が挙げられ、3~60モル%が好ましい。
樹脂Pは、スルトン(環状スルホン酸エステル)構造を有する繰り返し単位(以下、「繰り返し単位(b)」ともいう。)を有していてもよい。
繰り返し単位(b)としては、(メタ)アクリル酸誘導体モノマーに由来する繰り返し単位であることが好ましい。
繰り返し単位(b)は、1種単独で用いてもよく、2種以上を併用していてもよいが、1種単独で用いることが好ましい。
上記樹脂Pの全繰り返し単位に対する、上記繰り返し単位(b)の含有量は、繰り返し単位(b)が有する構造にもよるが、例えば、3~80モル%が挙げられ、3~60モル%が好ましい。
樹脂Pは、下記一般式(III′)で表されるスルトン構造を有する繰り返し単位を含有することが好ましい。
R82で表されるスルトン構造を有する1価の有機基は、スルトン構造を有していれば限定されるものではなく、具体例として上述した一般式(SL1-1)及び(SL1-2)で表されるスルトン構造が挙げられる。また、(SL1-1)及び(SL1-2)におけるn2は2以下のものがより好ましい。
また、R82は無置換のスルトン構造を有する1価の有機基、或いはメチル基、シアノ基又はアルコキシカルボニル基を置換基として有するスルトン構造を有する1価の有機基が好ましく、シアノ基を置換基として有するスルトン構造(シアノスルトン)を有する1価の有機基がより好ましい。
樹脂Pは、カーボネート構造を有する繰り返し単位を有していてもよい。
カーボネート構造(環状炭酸エステル構造)は、環を構成する原子群として-O-C(=O)-O-で表される結合を含む環を有する構造である。環を構成する原子群として-O-C(=O)-O-で表される結合を含む環は、5~7員環であることが好ましく、5員環であることが最も好ましい。このような環は、他の環と縮合し、縮合環を形成していてもよい。
樹脂Pは、カーボネート構造(環状炭酸エステル構造)を有する繰り返し単位として、下記一般式(A-1)で表される繰り返し単位を含有することが好ましい。
RA 19は、各々独立して、水素原子又は鎖状炭化水素基を表す。
Aは、単結合、2価若しくは3価の鎖状炭化水素基、2価若しくは3価の脂環式炭化水素基又は2価若しくは3価の芳香族炭化水素基を表し、Aが3価の場合、Aに含まれる炭素原子と環状炭酸エステルを構成する炭素原子とが結合されて、環構造が形成されている。
nAは2~4の整数を表す。
RA 19は、各々独立して、水素原子又は鎖状炭化水素基を表す。RA 19で表される鎖状炭化水素基は、炭素数1~5の鎖状炭化水素基であることが好ましい。「炭素数1~5の鎖状炭化水素基」としては、例えば、メチル基、エチル基、プロピル基、ブチル基等の炭素数1~5の直鎖状アルキル基;イソプロピル基、イソブチル基、t-ブチル基等の炭素数3~5の分岐状アルキル基;等を挙げることができる。鎖状炭化水素基はヒドロキシル基等の置換基を有していてもよい。
RA 19は、水素原子を表すことが最も好ましい。
nAは、2又は3であることが好ましく、2であることがより好ましい。
上記2価若しくは3価の鎖状炭化水素基は、炭素数が1~30である2価若しくは3価の鎖状炭化水素基であることが好ましい。
上記2価若しくは3価の脂環式炭化水素基は、炭素数が3~30である2価若しくは3価の脂環式炭化水素基であることが好ましい。
上記2価若しくは3価の芳香族炭化水素基は、炭素数が6~30である2価若しくは3価の芳香族炭化水素基であることが好ましい。
なお、以下の具体例中のRA 1は、一般式(A-1)におけるRA 1と同義である。
樹脂Pにおいて、カーボネート構造(環状炭酸エステル構造)を有する繰り返し単位(好ましくは、一般式(A-1)で表される繰り返し単位)の含有率は、樹脂Pを構成する全繰り返し単位に対して、3~80モル%であることが好ましく、3~60モル%であることがより好ましく、3~30モル%であることが更に好ましい。
上記樹脂Pは、その他の繰り返し単位を含んでいてもよい。
例えば、樹脂Pは、水酸基又はシアノ基を有する繰り返し単位を含んでいてもよい。このような繰り返し単位としては、例えば、特開2014-098921号公報の段落<0081>~<0084>に記載された繰り返し単位が挙げられる。
また、樹脂Pは、アルカリ可溶性基を有する繰り返し単位を有してもよい。アルカリ可溶性基としてはカルボキシル基、スルホンアミド基、スルホニルイミド基、ビススルホニルイミド基、α位が電子求引性基で置換された脂肪族アルコール(例えばヘキサフルオロイソプロパノール基)が挙げられる。アルカリ可溶性基を有する繰り返し単位としては、例えば、特開2014-098921号公報の段落<0085>~<0086>に記載された繰り返し単位が挙げられる。
また、樹脂Pは、更に極性基(例えば、アルカリ可溶性基、水酸基、シアノ基等)を持たない脂環炭化水素構造を有し、酸分解性を示さない繰り返し単位を有することができる。このような繰り返し単位としては、例えば、特開2014-106299号公報の段落<0114>~<0123>に記載された繰り返し単位が挙げられる。
また、樹脂Pは、例えば、特開2009-258586号公報の段落<0045>~<0065>に記載された繰り返し単位を含んでいてもよい。
本発明の組成物に用いられる樹脂Pは、上記の繰り返し単位以外に、様々な繰り返し単位を有することができる。このような繰り返し単位としては、下記の単量体に相当する繰り返し単位を挙げることができるが、これらに限定されない。
このような単量体として、例えばアクリル酸エステル類、メタクリル酸エステル類、アクリルアミド類、メタクリルアミド類、アリル化合物、ビニルエーテル類、ビニルエステル類等から選ばれる付加重合性不飽和結合を1個有する化合物等を挙げることができる。
その他にも、上記種々の繰り返し構造単位に相当する単量体と共重合可能である付加重合性の不飽和化合物であれば、共重合されていてもよい。
本発明の組成物に用いられる樹脂Pにおいて、各繰り返し構造単位の含有モル比は、適宜設定される。
樹脂Pは、上述したように、繰り返し単位Q1、及び、繰り返し単位Q2を有し、かつ、繰り返し単位Q2の含有量が20モル%以上であれば特に限定されないが、更に、上述した、繰り返し単位Q1とは異なるラクトン構造を有する繰り返し単位を有することが好ましい。
より好ましくは、樹脂Pは、繰り返し単位Q1と、繰り返し単位Q2と、繰り返し単位Q1とは異なるラクトン構造を有する繰り返し単位とのみからなる樹脂であることが好ましい。
樹脂Pにおける重量平均分子量(Mw)と数平均分子量(Mn)との比(Mw/Mn)である分散度(分子量分布)は、通常1.0~3.0であり、好ましくは1.0~2.6、より好ましくは1.0~2.0、更に好ましくは1.1~2.0の範囲である。分子量分布が小さいものほど、解像度、レジスト形状が優れ、且つレジストパターンの側壁がスムーズであり、ラフネス性に優れる。
また、樹脂Pは、1種単独で使用してもよいし、2種以上を併用してもよい。
本発明の組成物は、活性光線又は放射線の照射により酸を発生する化合物(以下、「酸発生剤」ともいう。)を含有する。酸発生剤としては、特に限定されないが、活性光線又は放射線の照射により有機酸を発生する化合物であることが好ましい。
酸発生剤としては、光カチオン重合の光開始剤、光ラジカル重合の光開始剤、色素類の光消色剤、光変色剤、あるいはマイクロレジスト等に使用されている、活性光線又は放射線の照射により酸を発生する公知の化合物及びそれらの混合物を適宜に選択して使用することができ、例えば、特開2010-61043号公報の段落<0039>~<0103>に記載されている化合物、特開2013-4820号公報の段落<0284>~<0389>に記載されている化合物などが挙げられるが、本発明はこれに限定されない。
たとえば、ジアゾニウム塩、ホスホニウム塩、スルホニウム塩、ヨードニウム塩、イミドスルホネート、オキシムスルホネート、ジアゾジスルホン、ジスルホン、o-ニトロベンジルスルホネートを挙げることができる。
一般式(3)中、
Xfは、各々独立に、フッ素原子、又は、少なくとも一つのフッ素原子で置換されたアルキル基を表す。
R4及びR5は、各々独立に、水素原子、フッ素原子、アルキル基、又は、少なくとも一つのフッ素原子で置換されたアルキル基を表し、複数存在する場合のR4、R5は、それぞれ同一でも異なっていてもよい。
Lは、2価の連結基を表し、複数存在する場合のLは同一でも異なっていてもよい。
Wは、環状構造を含む有機基を表す。
oは、1~3の整数を表す。pは、0~10の整数を表す。qは、0~10の整数を表す。
Xfは、好ましくは、フッ素原子又は炭素数1~4のパーフルオロアルキル基である。Xfは、フッ素原子又はCF3であることがより好ましい。特に、双方のXfがフッ素原子であることが好ましい。
R4及びR5としてのアルキル基は、置換基を有していてもよく、炭素数1~4のものが好ましい。R4及びR5は、好ましくは水素原子である。
少なくとも一つのフッ素原子で置換されたアルキル基の具体例および好適な態様は一般式(3)中のXfの具体例および好適な態様と同じである。
2価の連結基としては、例えば、-COO-、-OCO-、-CONH-、-NHCO-、-CO-、-O-、-S-、-SO-、-SO2-、アルキレン基(好ましくは炭素数1~6)、シクロアルキレン基(好ましくは炭素数3~10)、アルケニレン基(好ましくは炭素数2~6)又はこれらの複数を組み合わせた2価の連結基などが挙げられる。これらの中でも、-COO-、-OCO-、-CONH-、-NHCO-、-CO-、-O-、-SO2-、-COO-アルキレン基-、-OCO-アルキレン基-、-CONH-アルキレン基-又は-NHCO-アルキレン基-が好ましく、-COO-、-OCO-、-CONH-、-SO2-、-COO-アルキレン基-又は-OCO-アルキレン基-がより好ましい。
環状の有機基としては、例えば、脂環基、アリール基、及び複素環基が挙げられる。
脂環基は、単環式であってもよく、多環式であってもよい。単環式の脂環基としては、例えば、シクロペンチル基、シクロヘキシル基、及びシクロオクチル基などの単環のシクロアルキル基が挙げられる。多環式の脂環基としては、例えば、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及びアダマンチル基などの多環のシクロアルキル基が挙げられる。中でも、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及びアダマンチル基などの炭素数7以上のかさ高い構造を有する脂環基が、PEB(露光後加熱)工程での膜中拡散性の抑制及びMEEF(Mask Error Enhancement Factor)の向上の観点から好ましい。
複素環基は、単環式であってもよく、多環式であってもよいが、多環式の方がより酸の拡散を抑制可能である。また、複素環基は、芳香族性を有していてもよく、芳香族性を有していなくてもよい。芳香族性を有している複素環としては、例えば、フラン環、チオフェン環、ベンゾフラン環、ベンゾチオフェン環、ジベンゾフラン環、ジベンゾチオフェン環、及びピリジン環が挙げられる。芳香族性を有していない複素環としては、例えば、テトラヒドロピラン環、ラクトン環、スルトン環及びデカヒドロイソキノリン環が挙げられる。複素環基における複素環としては、フラン環、チオフェン環、ピリジン環、又はデカヒドロイソキノリン環が特に好ましい。また、ラクトン環及びスルトン環の例としては、前述の樹脂Pにおいて例示したラクトン構造及びスルトン構造が挙げられる。
一態様において、一般式(3)中のoが1~3の整数であり、pが1~10の整数であり、qが0であることが好ましい。Xfは、フッ素原子であることが好ましく、R4及びR5は共に水素原子であることが好ましく、Wは多環式の炭化水素基であることが好ましい。oは1又は2であることがより好ましく、1であることが更に好ましい。pが1~3の整数であることがより好ましく、1又は2であることが更に好ましく、1が特に好ましい。Wは多環のシクロアルキル基であることがより好ましく、アダマンチル基又はジアマンチル基であることが更に好ましい。
一般式(3)中、X+は、カチオンを表す。
X+は、カチオンであれば特に制限されないが、好適な態様としては、例えば、後述する一般式(ZI)、(ZII)又は(ZIII)中のカチオン(Z-以外の部分)が挙げられる。
特定酸発生剤の好適な態様としては、例えば、下記一般式(ZI)、(ZII)又は(ZIII)で表される化合物が挙げられる。
R201、R202及びR203は、各々独立に、有機基を表す。
R201、R202及びR203としての有機基の炭素数は、一般的に1~30、好ましくは1~20である。
また、R201~R203のうち2つが結合して環構造を形成してもよく、環内に酸素原子、硫黄原子、エステル結合、アミド結合、カルボニル基を含んでいてもよい。R201~R203の内の2つが結合して形成する基としては、アルキレン基(例えば、ブチレン基、ペンチレン基)を挙げることができる。
Z-は、一般式(3)中のアニオンを表し、具体的には、下記のアニオンを表す。
なお、一般式(ZI)で表される構造を複数有する化合物であってもよい。例えば、一般式(ZI)で表される化合物のR201~R203の少なくとも1つが、一般式(ZI)で表されるもうひとつの化合物のR201~R203の少なくとも一つと、単結合又は連結基を介して結合した構造を有する化合物であってもよい。
化合物(ZI-4)は、下記一般式(ZI-4)で表される。
R13は水素原子、フッ素原子、水酸基、アルキル基、シクロアルキル基、アルコキシ基、アルコキシカルボニル基、又はシクロアルキル基を有する基を表す。これらの基は置換基を有してもよい。
R14は、複数存在する場合は各々独立して、水酸基、アルキル基、シクロアルキル基、アルコキシ基、アルコキシカルボニル基、アルキルカルボニル基、アルキルスルホニル基、シクロアルキルスルホニル基、又はシクロアルキル基を有する基を表す。これらの基は置換基を有してもよい。
R15は各々独立して、アルキル基、シクロアルキル基又はナフチル基を表す。これらの基は置換基を有してもよい。2個のR15が互いに結合して環を形成してもよい。2個のR15が互いに結合して環を形成するとき、環骨格内に、酸素原子、窒素原子などのヘテロ原子を含んでもよい。一態様において、2個のR15がアルキレン基であり、互いに結合して環構造を形成することが好ましい。
lは0~2の整数を表す。
rは0~8の整数を表す。
Z-は、一般式(3)中のアニオンを表し、具体的には、上述のとおりである。
本発明における一般式(ZI-4)で表される化合物のカチオンとしては、特開2010-256842号公報の段落<0121>、<0123>、<0124>、及び、特開2011-76056号公報の段落<0127>、<0129>、<0130>等に記載のカチオンを挙げることができる。
一般式(ZII)、(ZIII)中、R204~R207は、各々独立に、アリール基、アルキル基又はシクロアルキル基を表す。
R204~R207のアリール基としてはフェニル基、ナフチル基が好ましく、更に好ましくはフェニル基である。R204~R207のアリール基は、酸素原子、窒素原子、硫黄原子等を有する複素環構造を有するアリール基であってもよい。複素環構造を有するアリール基の骨格としては、例えば、ピロール、フラン、チオフェン、インドール、ベンゾフラン、ベンゾチオフェン等を挙げることができる。
R204~R207におけるアルキル基及びシクロアルキル基としては、好ましくは、炭素数1~10の直鎖又は分岐アルキル基(例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基)、炭素数3~10のシクロアルキル基(シクロペンチル基、シクロヘキシル基、ノルボルニル基)を挙げることができる。
Z-は、一般式(3)中のアニオンを表し、具体的には、上述のとおりである。
酸発生剤が、低分子化合物の形態である場合、分子量は3000以下が好ましく、2000以下がより好ましく、1000以下が更に好ましい。
酸発生剤が、重合体の一部に組み込まれた形態である場合、前述した樹脂Pの一部に組み込まれてもよく、樹脂Pとは異なる樹脂に組み込まれてもよい。
酸発生剤は、公知の方法で合成することができ、例えば、特開2007-161707号公報に記載の方法に準じて合成することができる。
酸発生剤は、1種類単独又は2種類以上を組み合わせて使用することができる。
酸発生剤の組成物中の含有量(複数種存在する場合はその合計)は、組成物の全固形分を基準として、0.1~30質量%が好ましく、より好ましくは0.5~25質量%、更に好ましくは3~20質量%、特に好ましくは3~15質量%である。
また、酸発生剤が上記一般式(ZI-4)により表される特定酸発生剤である場合(複数種存在する場合はその合計)には、その含有量は、組成物の全固形分を基準として、5~35質量%が好ましく、8~30質量%がより好ましく、9~30質量%が更に好ましく、9~25質量%が特に好ましい。
本発明の組成物は、疎水性樹脂(以下、「疎水性樹脂(D)」又は単に「樹脂(D)」ともいう。)を含有してもよい。なお、疎水性樹脂(D)は樹脂Pとは異なることが好ましい。
疎水性樹脂(D)は、界面に偏在するように設計されることが好ましいが、界面活性剤とは異なり、必ずしも分子内に親水基を有する必要はなく、極性/非極性物質を均一に混合することに寄与しなくてもよい。
疎水性樹脂を添加することの効果として、水に対するレジスト膜表面の静的/動的な接触角の制御、液浸液追随性の向上、アウトガスの抑制などを挙げることができる。
疎水性樹脂(D)が、フッ素原子及び/又は珪素原子を含む場合、疎水性樹脂(D)に於ける上記フッ素原子及び/又は珪素原子は、樹脂の主鎖中に含まれていてもよく、側鎖中に含まれていてもよい。
フッ素原子を有するアルキル基(好ましくは炭素数1~10、より好ましくは炭素数1~4)は、少なくとも1つの水素原子がフッ素原子で置換された直鎖又は分岐アルキル基であり、更にフッ素原子以外の置換基を有していてもよい。
フッ素原子を有するシクロアルキル基及びフッ素原子を有するアリール基は、それぞれ、1つの水素原子がフッ素原子で置換されたシクロアルキル基及びフッ素原子を有するアリール基であり、更にフッ素原子以外の置換基を有していてもよい。
R57~R68は、各々独立に、水素原子、フッ素原子又はアルキル基(直鎖若しくは分岐)を表す。但し、R57~R61の少なくとも1つ、R62~R64の少なくとも1つ、及びR65~R68の少なくとも1つは、各々独立に、フッ素原子又は少なくとも1つの水素原子がフッ素原子で置換されたアルキル基(好ましくは炭素数1~4)を表す。
R57~R61及びR65~R67は、全てがフッ素原子であることが好ましい。R62、R63及びR68は、少なくとも1つの水素原子がフッ素原子で置換されたアルキル基(好ましくは炭素数1~4)が好ましく、炭素数1~4のパーフルオロアルキル基であることが更に好ましい。R62とR63は、互いに連結して環を形成してもよい。
フッ素原子又は珪素原子を有する繰り返し単位の例としては、US2012/0251948A1〔0519〕に例示されたものを挙げることが出来る。
ここで、疎水性樹脂(D)中の側鎖部分が有するCH3部分構造(以下、単に「側鎖CH3部分構造」ともいう。)には、エチル基、プロピル基等が有するCH3部分構造を包含するものである。
一方、疎水性樹脂(D)の主鎖に直接結合しているメチル基(例えば、メタクリル酸構造を有する繰り返し単位のα-メチル基)は、主鎖の影響により疎水性樹脂(D)の表面偏在化への寄与が小さいため、本発明におけるCH3部分構造に包含されないものとする。
一方、C-C主鎖から何らかの原子を介して存在するCH3部分構造は、本発明におけるCH3部分構造に該当するものとする。例えば、R11がエチル基(CH2CH3)である場合、本発明におけるCH3部分構造を「1つ」有するものとする。
R11~R14は、各々独立に、側鎖部分を表す。
側鎖部分のR11~R14としては、水素原子、1価の有機基などが挙げられる。
R11~R14についての1価の有機基としては、アルキル基、シクロアルキル基、アリール基、アルキルオキシカルボニル基、シクロアルキルオキシカルボニル基、アリールオキシカルボニル基、アルキルアミノカルボニル基、シクロアルキルアミノカルボニル基、アリールアミノカルボニル基などが挙げられ、これらの基は、更に置換基を有していてもよい。
Xb1は、水素原子又はメチル基であることが好ましい。
R2としては、1つ以上のCH3部分構造を有する、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アリール基、及び、アラルキル基が挙げられる。上記のシクロアルキル基、アルケニル基、シクロアルケニル基、アリール基、及び、アラルキル基は、更に、置換基としてアルキル基を有していてもよい。
R2は、1つ以上のCH3部分構造を有する、アルキル基又はアルキル置換シクロアルキル基が好ましい。
R2としての1つ以上のCH3部分構造を有する酸に安定な有機基は、CH3部分構造を2個以上10個以下有することが好ましく、2個以上8個以下有することがより好ましい。
一般式(II)で表される繰り返し単位の好ましい具体例を以下に挙げる。なお、本発明はこれに限定されない。
以下、一般式(III)で表される繰り返し単位について詳細に説明する。
Xb2のアルキル基は、炭素数1~4のものが好ましく、メチル基、エチル基、プロピル基、ヒドロキシメチル基又はトリフルオロメチル基等が挙げられるが、水素原子である事が好ましい。
Xb2は、水素原子であることが好ましい。
R3は、酸に対して安定な有機基であるため、より具体的には、酸分解性基を有さない有機基であることが好ましい。
R3としての1つ以上のCH3部分構造を有する酸に安定な有機基は、CH3部分構造を1個以上10個以下有することが好ましく、1個以上8個以下有することがより好ましく、1個以上4個以下有することが更に好ましい。
nは1から5の整数を表し、1~3の整数を表すことがより好ましく、1又は2を表すことが更に好ましい。
(x)酸基、
(y)ラクトン構造を有する基、酸無水物基、又は酸イミド基、
(z)酸の作用により分解する基
好ましい酸基としては、フッ素化アルコール基(好ましくはヘキサフルオロイソプロパノール)、スルホンイミド基、ビス(アルキルカルボニル)メチレン基が挙げられる。
酸基(x)を有する繰り返し単位の含有量は、疎水性樹脂(D)中の全繰り返し単位に対し、1~50モル%が好ましく、より好ましくは3~35モル%、更に好ましくは5~20モル%である。
酸基(x)を有する繰り返し単位の具体例を以下に示すが、本発明は、これに限定されない。式中、Rxは水素原子、CH3、CF3、又は、CH2OHを表す。
これらの基を含んだ繰り返し単位は、例えば、アクリル酸エステル及びメタクリル酸エステルによる繰り返し単位等の、樹脂の主鎖に直接この基が結合している繰り返し単位である。或いは、この繰り返し単位は、この基が連結基を介して樹脂の主鎖に結合している繰り返し単位であってもよい。或いは、この繰り返し単位は、この基を有する重合開始剤又は連鎖移動剤を重合時に用いて、樹脂の末端に導入されていてもよい。
ラクトン構造を有する基を有する繰り返し単位としては、例えば、先に樹脂Pの項で説明したラクトン構造を有する繰り返し単位と同様のものが挙げられる。
疎水性樹脂(D)は、更に、上述した繰り返し単位とは別の繰り返し単位を有していてもよい。
また、疎水性樹脂(D)は、1種で使用してもよいし、複数併用してもよい。
疎水性樹脂(D)の組成物中の含有量は、本発明の組成物中の全固形分に対し、0.01~10質量%が好ましく、0.05~8質量%がより好ましい。
本発明の組成物は、酸拡散制御剤を含有することが好ましい。酸拡散制御剤は、露光時に酸発生剤等から発生する酸をトラップし、余分な発生酸による、未露光部における酸分解性樹脂の反応を抑制するクエンチャーとして作用するものである。酸拡散制御剤としては、塩基性化合物、窒素原子を有し、酸の作用により脱離する基を有する低分子化合物、又は、酸発生剤に対して相対的に弱酸となるオニウム塩を使用することができる。
R200、R201及びR202は、同一でも異なってもよく、水素原子、アルキル基(好ましくは炭素数1~20)、シクロアルキル基(好ましくは炭素数3~20)又はアリール基(炭素数6~20)を表し、ここで、R201とR202は、互いに結合して環を形成してもよい。
R203、R204、R205及びR206は、同一でも異なってもよく、炭素数1~20個のアルキル基を表す。
これら一般式(A)及び(E)中のアルキル基は、無置換であることがより好ましい。
好ましい化合物の具体例としては、米国特許出願公開第2012/0219913号明細書の段落<0379>に例示された化合物を挙げることができる。
好ましい塩基性化合物として、更に、フェノキシ基を有するアミン化合物、フェノキシ基を有するアンモニウム塩化合物、スルホン酸エステル基を有するアミン化合物及びスルホン酸エステル基を有するアンモニウム塩化合物を挙げることができる。
これらの塩基性化合物は、1種類を単独で用いてもよく、2種類以上を組み合わせて用いてもよい。
酸発生剤と塩基性化合物との組成物中の使用割合は、モル比(酸発生剤/塩基性化合物)で、2.5~300が好ましく、より好ましくは5.0~200、更に好ましくは7.0~150である。
酸の作用により脱離する基として、アセタール基、カルボネート基、カルバメート基、3級エステル基、3級水酸基、ヘミアミナールエーテル基が好ましく、カルバメート基、ヘミアミナールエーテル基であることが特に好ましい。
化合物(C)の分子量は、100~1000が好ましく、100~700がより好ましく、100~500が特に好ましい。
化合物(C)は、窒素原子上に保護基を有するカルバメート基を有してもよい。カルバメート基を構成する保護基としては、下記一般式(d-1)で表すことができる。
Rbは、各々独立に、水素原子、アルキル基(好ましくは炭素数1~10)、シクロアルキル基(好ましくは炭素数3~30)、アリール基(好ましくは炭素数3~30)、アラルキル基(好ましくは炭素数1~10)、又はアルコキシアルキル基(好ましくは炭素数1~10)を表す。Rbは相互に連結して環を形成していてもよい。
Rbが示すアルキル基、シクロアルキル基、アリール基、アラルキル基は、ヒドロキシル基、シアノ基、アミノ基、ピロリジノ基、ピペリジノ基、モルホリノ基、オキソ基等の官能基、アルコキシ基、ハロゲン原子で置換されていてもよい。Rbが示すアルコキシアルキル基についても同様である。
2つのRbが相互に連結して形成する環としては、脂環式炭化水素基、芳香族炭化水素基、複素環式炭化水素基若しくはその誘導体等が挙げられる。
一般式(d-1)で表される基の具体的な構造としては、米国特許出願公開第2012/0135348号明細書の段落<0466>に開示された構造を挙げることができるが、これに限定されない。
Rbは、上記一般式(d-1)におけるRbと同義であり、好ましい例も同様である。
lは0~2の整数を表し、mは1~3の整数を表し、l+m=3を満たす。
一般式(6)において、Raとしてのアルキル基、シクロアルキル基、アリール基、アラルキル基は、Rbとしてのアルキル基、シクロアルキル基、アリール基、アラルキル基が置換されていてもよい基として前述した基と同様な基で置換されていてもよい。
本発明における特に好ましい化合物(C)の具体例としては、米国特許出願公開第2012/0135348号明細書の段落<0475>に開示された化合物を挙げることができるが、これに限定されない。
本発明において、酸の作用により脱離する基を窒素原子上に有する低分子化合物(C)は、一種単独でも又は2種以上を混合しても使用することができる。
本発明の組成物における化合物(C)の含有量は、組成物の全固形分を基準として、0.001~20質量%であることが好ましく、より好ましくは0.001~10質量%、更に好ましくは0.01~5質量%である。
酸発生剤と、酸発生剤から生じた酸に対して相対的に弱酸である酸を発生するオニウム塩を混合して用いた場合、活性光線性又は放射線の照射により酸発生剤から生じた酸が未反応の弱酸アニオンを有するオニウム塩と衝突すると、塩交換により弱酸を放出して強酸アニオンを有するオニウム塩を生じる。この過程で強酸がより触媒能の低い弱酸に交換されるため、見かけ上、酸が失活して酸拡散の制御を行うことができる。
一般式(d1‐2)で表される化合物のアニオン部の好ましい例としては、特開2012-242799号公報の段落〔0201〕に例示された構造を挙げることが出来る。
一般式(d1‐3)で表される化合物のアニオン部の好ましい例としては、特開2012-242799号公報の段落〔0209〕及び〔0210〕に例示された構造を挙げることが出来る。
化合物(CA)としては、下記一般式(C-1)~(C-3)のいずれかで表される化合物であることが好ましい。
R1、R2、R3は、炭素数1以上の置換基を表す。
L1は、カチオン部位とアニオン部位を連結する2価の連結基又は単結合を表す。
-X-は、-COO-、-SO3 -、-SO2 -、-N--R4から選択されるアニオン部位を表す。R4は、隣接するN原子との連結部位に、カルボニル基:-C(=O)-、スルホニル基:-S(=O)2-、スルフィニル基:-S(=O)-を有する1価の置換基を表す。
R1、R2、R3、R4、L1は互いに結合して環構造を形成してもよい。また、(C-3)において、R1~R3のうち2つを合わせて、N原子と2重結合を形成してもよい。
一般式(C-1)で表される化合物の好ましい例としては、特開2013-6827号公報の段落〔0037〕~〔0039〕及び特開2013-8020号公報の段落〔0027〕~〔0029〕に例示された化合物を挙げることが出来る。
一般式(C-2)で表される化合物の好ましい例としては、特開2012-189977号公報の段落〔0012〕~〔0013〕に例示された化合物を挙げることが出来る。
一般式(C-3)で表される化合物の好ましい例としては、特開2012-252124号公報の段落〔0029〕~〔0031〕に例示された化合物を挙げることが出来る。
本発明の組成物は、通常、溶剤を含有する。
組成物を調製する際に使用することができる溶剤としては、例えば、アルキレングリコールモノアルキルエーテルカルボキシレート、アルキレングリコールモノアルキルエーテル、乳酸アルキルエステル、アルコキシプロピオン酸アルキル、環状ラクトン(好ましくは炭素数4~10)、環を有してもよいモノケトン化合物(好ましくは炭素数4~10)、アルキレンカーボネート、アルコキシ酢酸アルキル、ピルビン酸アルキル等の有機溶剤を挙げることができる。
これらの溶剤の具体例は、米国特許出願公開2008/0187860号明細書<0441>~<0455>に記載のものを挙げることができる。
水酸基を含有する溶剤、水酸基を含有しない溶剤としては前述の例示化合物が適宜選択可能であるが、水酸基を含有する溶剤としては、アルキレングリコールモノアルキルエーテル、乳酸アルキル等が好ましく、プロピレングリコールモノメチルエーテル(PGME、別名1-メトキシ-2-プロパノール)、2-ヒドロキシイソ酪酸メチル、乳酸エチルがより好ましい。また、水酸基を含有しない溶剤としては、アルキレングリコールモノアルキルエーテルアセテート、アルキルアルコキシプロピオネート、環を含有してもよいモノケトン化合物、環状ラクトン、酢酸アルキルなどが好ましく、これらの内でもプロピレングリコールモノメチルエーテルアセテート(PGMEA、別名1-メトキシ-2-アセトキシプロパン)、エチルエトキシプロピオネート、2-ヘプタノン、γ-ブチロラクトン、シクロヘキサノン、酢酸ブチルが特に好ましく、プロピレングリコールモノメチルエーテルアセテート、エチルエトキシプロピオネート、2-ヘプタノンが最も好ましい。
水酸基を含有する溶剤と水酸基を含有しない溶剤との混合比(質量比)は、1/99~99/1、好ましくは10/90~90/10、更に好ましくは20/80~60/40である。水酸基を含有しない溶剤を50質量%以上含有する混合溶剤が塗布均一性の点で特に好ましい。
溶剤は、プロピレングリコールモノメチルエーテルアセテートを含むことが好ましく、プロピレングリコールモノメチルエーテルアセテート単独溶剤、又は、プロピレングリコールモノメチルエーテルアセテートを含有する2種類以上の混合溶剤であることがより好ましい。
本発明の組成物は、更に界面活性剤を含有してもしなくてもよく、含有する場合、フッ素系及び/又はシリコン系界面活性剤(フッ素系界面活性剤、シリコン系界面活性剤、フッ素原子とケイ素原子との両方を有する界面活性剤)が好ましい。
フッ素系及び/又はシリコン系界面活性剤として、米国特許出願公開第2008/0248425号明細書の段落<0276>に記載の界面活性剤が挙げることができる。
また、本発明では、米国特許出願公開第2008/0248425号明細書の段落<0280>に記載の、フッ素系及び/又はシリコン系界面活性剤以外の他の界面活性剤を使用することもできる。
本発明の組成物が界面活性剤を含有する場合、界面活性剤の含有量は、組成物の全固形分に対して、好ましくは0.0001~2質量%、より好ましくは0.0005~1質量%である。
一方、界面活性剤の添加量を、組成物の全量(溶剤を除く)に対して、10ppm以下とすることで、疎水性樹脂の表面偏在性があがり、それにより、レジスト膜表面をより疎水的にすることができ、液浸露光時の水追随性を向上させることができる。
本発明の組成物は、カルボン酸オニウム塩を含有してもしなくてもよい。このようなカルボン酸オニウム塩は、米国特許出願公開2008/0187860号明細書<0605>~<0606>に記載のものを挙げることができる。
これらのカルボン酸オニウム塩は、スルホニウムヒドロキシド、ヨードニウムヒドロキシド、アンモニウムヒドロキシドとカルボン酸を適当な溶剤中酸化銀と反応させることによって合成できる。
本発明の組成物には、必要に応じて更に、酸増殖剤、染料、可塑剤、光増感剤、光吸収剤、アルカリ可溶性樹脂、溶解阻止剤及び現像液に対する溶解性を促進させる化合物(例えば、分子量1000以下のフェノール化合物、カルボキシル基を有する脂環族、又は脂肪族化合物)等を含有させることができる。
カルボキシル基を有する脂環族、又は脂肪族化合物の具体例としてはコール酸、デオキシコール酸、リトコール酸などのステロイド構造を有するカルボン酸誘導体、アダマンタンカルボン酸誘導体、アダマンタンジカルボン酸、シクロヘキサンカルボン酸、シクロヘキサンジカルボン酸などが挙げられるがこれらに限定されない。
本発明における組成物の固形分濃度は、通常1.0~10質量%であり、好ましくは、2.0~5.7質量%、更に好ましくは2.0~5.3質量%である。固形分濃度を上記範囲とすることで、レジスト溶液を基板上に均一に塗布することができ、更にはラインウィズスラフネスに優れたレジストパターンを形成することが可能になる。その理由は明らかではないが、恐らく、固形分濃度を10質量%以下、好ましくは5.7質量%以下とすることで、レジスト溶液中での素材、特には光酸発生剤の凝集が抑制され、その結果として、均一なレジスト膜が形成できたものと考えられる。
固形分濃度とは、組成物の総質量に対する、溶剤を除く他のレジスト成分の質量の質量百分率である。
次に、本発明のパターン形成方法について説明する。
本発明のパターン形成方法は、
(i)本発明の組成物によって基板上に膜(感活性光線又は感放射線性樹脂組成物膜、組成物膜、レジスト膜)を形成する工程、
(ii)上記膜に活性光線又は放射線を照射(露光)する工程(露光工程)、及び
(iii)有機溶剤を含有する現像液を用いて、上記活性光線又は放射線を照射した膜を現像する工程(現像工程)、
を少なくとも有する。
本発明のパターン形成方法は、(ii)露光工程の後に、(iv)加熱工程を含むことが好ましい。
本発明のパターン形成方法は、(ii)露光工程を、複数回含んでいてもよい。
本発明のパターン形成方法は、(iv)加熱工程を、複数回含んでいてもよい。
更に、必要に応じて、レジスト膜と基板との間に反射防止膜を形成させてもよい。反射防止膜としては、公知の有機系、無機系の反射防止膜を適宜用いることができる。
また、露光工程の後かつ現像工程の前に、露光後加熱工程(PEB;Post Exposure Bake)を含むことも好ましい。
加熱温度はPB、PEB共に70~130℃で行うことが好ましく、80~120℃で行うことがより好ましい。
加熱時間は30~300秒が好ましく、30~180秒がより好ましく、30~90秒が更に好ましい。
加熱は通常の露光機および現像機に備わっている手段で行うことができ、ホットプレート等を用いて行ってもよい。
ベークにより露光部の反応が促進され、感度やパターンプロファイルが改善する。
トップコートについては、特に限定されず、従来公知のトップコートを、従来公知の方法によって形成でき、例えば、特開2014-059543号公報の段落<0072>~<0082>の記載に基づいてトップコートを形成できる。
後述する現像工程において、有機溶剤を含有する現像液を使用する場合は、特開2013-61648号公報に記載された塩基性化合物を含有するトップコートをレジスト膜上に形成することが好ましい。
また、液浸露光方法以外によって露光を行う場合であっても、レジスト膜上にトップコートを形成してもよい。
アミド系溶剤としては、例えば、N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド、ヘキサメチルホスホリックトリアミド、1,3-ジメチル-2-イミダゾリジノン等が使用できる。
炭化水素系溶剤としては、例えば、トルエン、キシレンなどの芳香族炭化水素系溶剤;ペンタン、ヘキサン、オクタン、デカンなどの脂肪族炭化水素系溶剤;等が挙げられる。
すなわち、有機系現像液に対する有機溶剤の含有量は、現像液の全量に対して、90質量%以上100質量%以下であることが好ましく、95質量%以上100質量%以下であることが好ましい。
界面活性剤としては特に限定されないが、例えば、イオン性や非イオン性のフッ素系及び/又はシリコン系界面活性剤等を用いることができる。これらのフッ素及び/又はシリコン系界面活性剤として、例えば特開昭62-36663号公報、特開昭61-226746号公報、特開昭61-226745号公報、特開昭62-170950号公報、特開昭63-34540号公報、特開平7-230165号公報、特開平8-62834号公報、特開平9-54432号公報、特開平9-5988号公報、米国特許第5405720号明細書、同5360692号明細書、同5529881号明細書、同5296330号明細書、同5436098号明細書、同5576143号明細書、同5294511号明細書、同5824451号明細書記載の界面活性剤を挙げることができ、好ましくは、非イオン性の界面活性剤である。非イオン性の界面活性剤としては特に限定されないが、フッ素系界面活性剤又はシリコン系界面活性剤を用いることが更に好ましい。
本発明において、有機溶剤現像工程によって露光強度の弱い部分が除去されるが、更にアルカリ現像工程を行うことによって露光強度の強い部分も除去される。このように現像を複数回行う多重現像プロセスにより、中間的な露光強度の領域のみを溶解させずにパターン形成が行えるので、通常より微細なパターンを形成できる(特開2008-292975号公報<0077>と同様のメカニズム)。
有機溶剤を含む現像液を用いて現像する工程の後のリンス工程に用いるリンス液としては、レジストパターンを溶解しなければ特に制限はなく、一般的な有機溶剤を含む溶液を使用することができる。リンス液としては、炭化水素系溶剤、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、アミド系溶剤及びエーテル系溶剤からなる群より選択される少なくとも1種類の有機溶剤を含有するリンス液を用いることが好ましい。
炭化水素系溶剤、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、アミド系溶剤及びエーテル系溶剤の具体例としては、有機溶剤を含む現像液において説明したものと同様のものを挙げることができる。
リンス液としてエステル系溶剤を用いる場合には、エステル系溶剤(1種または2種以上)に加えて、グリコールエーテル系溶剤を用いてもよい。この場合の具体例としては、エステル系溶剤(好ましくは、酢酸ブチル)を主成分として、グリコールエーテル系溶剤(好ましくはプロピレングリコールモノメチルエーテル(PGME))を副成分として用いることが挙げられる。これにより、残渣欠陥が抑制される。
リンス液中の含水率は、10質量%以下が好ましく、より好ましくは5質量%以下、特に好ましくは3質量%以下である。含水率を10質量%以下にすることで、良好な現像特性を得ることができる。
リンス工程においては、有機溶剤を含む現像液を用いる現像を行ったウエハを上記の有機溶剤を含むリンス液を用いて洗浄処理する。洗浄処理の方法は特に限定されないが、たとえば、一定速度で回転している基板上にリンス液を吐出しつづける方法(回転塗布法)、リンス液が満たされた槽中に基板を一定時間浸漬する方法(ディップ法)、基板表面にリンス液を噴霧する方法(スプレー法)、などを適用することができ、この中でも回転塗布方法で洗浄処理を行い、洗浄後に基板を2000rpm~4000rpmの回転数で回転させ、リンス液を基板上から除去することが好ましい。また、リンス工程の後に加熱工程(Post Bake)を含むことも好ましい。ベークによりパターン間及びパターン内部に残留した現像液及びリンス液が除去される。リンス工程の後の加熱工程は、通常40~160℃、好ましくは70~95℃で、通常10秒~3分、好ましくは30秒から90秒間行う。
上記各種材料から金属等の不純物を除去する方法としては、例えば、フィルターを用いた濾過を挙げることができる。フィルター孔径としては、ポアサイズ10nm以下が好ましく、5nm以下がより好ましく、3nm以下が更に好ましい。フィルターの材質としては、ポリテトラフルオロエチレン製、ポリエチレン製、ナイロン製のフィルターが好ましい。フィルターは、有機溶剤であらかじめ洗浄したものを用いてもよい。フィルター濾過工程では、複数種類のフィルターを直列又は並列に接続して用いてもよい。複数種類のフィルターを使用する場合は、孔径及び/又は材質が異なるフィルターを組み合わせて使用してもよい。また、各種材料を複数回濾過してもよく、複数回濾過する工程が循環濾過工程であってもよい。
また、上記各種材料に含まれる金属等の不純物を低減する方法としては、各種材料を構成する原料として金属含有量が少ない原料を選択する、各種材料を構成する原料に対してフィルター濾過を行う、装置内をテフロン(登録商標)でライニングする等してコンタミネーションを可能な限り抑制した条件下で蒸留を行う等の方法を挙げることができる。各種材料を構成する原料に対して行うフィルター濾過における好ましい条件は、上記した条件と同様である。
フィルター濾過のほか、吸着材による不純物の除去を行ってもよく、フィルター濾過と吸着材を組み合わせて使用してもよい。吸着材としては、公知の吸着材を用いることができ、例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材を使用することができる。
本発明のパターン形成方法は、DSA(Directed Self-Assembly)におけるガイドパターン形成(例えば、ACS Nano Vol.4 No.8 Page4815-4823参照)にも用いることができる。
また、上記の方法によって形成されたレジストパターンは、例えば特開平3-270227号公報及び特開2013-164509号公報に開示されたスペーサープロセスの芯材(コア)として使用できる。
シクロヘキサノン 55.6質量部を窒素気流下、80℃に加熱した。この液を攪拌しながら、そこへ、下記構造式M-1で表されるモノマー 3.15質量部、下記構造式M-2で表されるモノマー 17.0質量部、下記構造式M-3で表されるモノマー 32.8質量部、シクロヘキサノン 103.3質量部、2,2’-アゾビスイソ酪酸ジメチル〔V-601、和光純薬工業(株)製〕2.30質量部の混合溶液を6時間かけて滴下した。滴下終了後の溶液を、更に、80℃で2時間攪拌し反応液を得た。反応液を放冷後、そこへ、シクロヘキサノン 141.2質量部を加え、多量のメタノール/水(質量比9:1)で再沈殿した。次いで、得られた固体をろ過し、真空乾燥することで、下記樹脂B-1を37.3質量部得た。
なお、合成例1と同様の操作を行い、後掲の樹脂B-2~B-12を合成した。
下記表1に示す成分を、同表に示す配合量(単位:質量部)で、同表に示す溶剤に溶解させた。それぞれの溶液が固形分濃度4質量%の溶液となるように調製した。さらに溶液を0.05μmのポアサイズを有するポリエチレンフィルターで濾過することで、レジスト組成物(実施例および比較例のレジスト組成物)を調製した。
なお、下記表1中、溶剤について、カッコ内の数値は質量比を表す。
(フォーカス許容度(DOF:Depth of Focus)の評価)
シリコンウエハ上に有機反射防止膜形成用組成物ARC29SR(日産化学社製)を塗布し、205℃で60秒間ベークし、膜厚95nmの反射防止膜を形成した。有機反射防止膜上にレジスト組成物を塗布し、100℃で60秒間ベーク(Pre Bake;PB)した。これにより、膜厚100nmのレジスト膜を得た。
得られたレジスト膜をArF液浸露光機(XT1700i;ASML社製、NA1.20、Annular、アウターシグマ0.80、インナーシグマ0.64)にて、ピッチ550nm、遮光部90nmのマスクを通して露光した。露光後のレジスト膜を100℃で60秒間ベーク(Post Exposure Bake;PEB)した後、有機系現像液(酢酸ブチル)を用いて現像することで、ホール径が45nmであるコンタクトホールパターンを形成した。形成されたコンタクトホールパターンにおいて、フォーカス方向に15nm刻みでフォーカス条件を変更して露光および現像を行った。得られる各パターンのホール径(CD)を線幅測長走査型電子顕微鏡SEM(S-9380;日立製作所株式会社製)にて測定し、CD変化を観測した。観測されたCDにおいて極大値に対し、45nm±10%を許容するフォーカス変動幅、すなわちフォーカス許容度(DOF)を算出した。表1に結果を示す。DOFは値が大きいほどフォーカスのズレに対するCD変動が小さいため性能が優れている。
なお、実施例12では、以下に示す樹脂を2.5質量%、以下に示すアミン化合物を0.5質量%、4-メチル-2-ペンタノール溶剤を97質量%含むトップコート組成物を用いて、レジスト膜上に厚さ100nmのトップコート層を設けた。
シリコンウエハ上に有機反射防止膜形成用組成物ARC29SR(日産化学社製)を塗布し、205℃で60秒間ベークを行い、膜厚95nmの有機反射防止膜を形成した。有機反射防止膜上に得られたレジスト組成物を塗布し、100℃で60秒間に亘ってベーク(PB:Prebake)した。これにより、膜厚100nmのレジスト膜を得た。
得られたレジスト膜をArF液浸露光機(ASML社製;XT1700i、NA1.20、C-Quad、アウターシグマ0.900、インナーシグマ0.812、XY偏向)を用い、線幅48nmの1:1ラインアンドスペースパターンの6%ハーフトーンマスクを通して露光した。液浸液としては超純水を用いた。その後、露光後のレジスト膜を100℃で60秒間加熱(PEB:Post Exposure Bake)した。次いで、酢酸ブチルで30秒間パドルして現像し、リンス液〔メチルイソブチルカルビノール(MIBC)〕で30秒間パドルしてリンスした。続いて、4000rpmの回転数で30秒間ウエハを回転させることにより、線幅48nmの1:1ラインアンドスペースのパターンを形成した。形成されたライン/スペース=1/1のラインパターン(線幅48nm)について線幅測長走査型電子顕微鏡SEM((株)日立製作所S-9380)で観察し、ラインパターンの長手方向のエッジ1μmの範囲について、線幅を50ポイント測定し、その測定ばらつきについて標準偏差を求め、3σ(単位:nm)を算出した。表1に結果を示す(LWR)。値が小さいほど良好な性能であることを示す。
なお、実施例12においては、DOF評価の場合と同様にして、トップコート層を設けた。
A1:プロピレングリコールモノメチルエーテルアセテート(PGMEA)
A2:シクロヘキサノン
A3:γ―ブチロラクトン
B1:プロピレングリコールモノメチルエーテル(PGME)
B2:乳酸エチル
なお、比較例1は、繰り返し単位Q2を有しない樹脂B-13を使用した例であり、比較例2は、繰り返し単位Q2の含有量が20モル%未満である樹脂B-14を使用した例であり、比較例3は、繰り返し単位Q1を有しない樹脂B-15を使用した例である。
また、繰り返し単位Q2の含有量が50モル%以上である樹脂B-1、B-4~B-7、及び、B-10を使用した実施例1、4~7および10は、DOF及びLWRが更に良好であった。
Claims (13)
- (i)感活性光線性又は感放射線性樹脂組成物によって基板上に感活性光線性又は感放射線性樹脂組成物膜を形成する工程、
(ii)前記膜に活性光線又は放射線を照射する工程、及び、
(iii)前記活性光線又は放射線が照射された膜を、有機溶剤を含有する現像液を用いて現像する工程、
を少なくとも有するパターン形成方法であって、
前記感活性光線性又は感放射線性樹脂組成物が、樹脂Pと、活性光線又は放射線の照射により酸を発生する化合物とを含有し、
前記樹脂Pが、下記一般式(q1)で表される繰り返し単位Q1、及び、下記一般式(q2)で表される繰り返し単位Q2を有し、
前記樹脂Pの全繰り返し単位に対する、前記繰り返し単位Q2の含有量が、20モル%以上である、パターン形成方法。
一般式(q1)中、R1は、水素原子又は炭素数1~20の有機基を表す。R2~R5は、それぞれ独立して、水素原子、フッ素原子、ヒドロキシ基又は炭素数1~20の有機基を表す。aは、1~6の整数を表す。但し、R2とR3、及びR4とR5は、互いに結合して、これらが結合している炭素原子と共に環員数3~10の環構造を形成していてもよい。
一般式(q2)中、R6は、水素原子又は炭素数1~20の有機基を表す。R7及びR8は、炭素数1~10の分岐構造を含んでよい鎖状のアルキル基を表す。R9は、炭素数1~10の分岐構造を含んでよいアルキル基又は炭素数3~14の単環式又は多環式のシクロアルキル基を表す。 - 前記一般式(q2)中、R9が、炭素数3~14の多環式シクロアルキル基を表す、請求項1に記載のパターン形成方法。
- 前記樹脂Pが、更に、前記繰り返し単位Q1とは異なるラクトン構造を有する繰り返し単位を有する、請求項1又は2に記載のパターン形成方法。
- 前記樹脂Pの全繰り返し単位に対する、前記繰り返し単位Q2の含有量が、40モル%以上である、請求項1~3のいずれか1項に記載のパターン形成方法。
- 前記樹脂Pの全繰り返し単位に対する、前記繰り返し単位Q2の含有量が、50モル%以上である、請求項4に記載のパターン形成方法。
- 前記樹脂Pが、前記繰り返し単位Q1と、前記繰り返し単位Q2と、前記繰り返し単位Q1とは異なるラクトン構造を有する繰り返し単位とのみからなる樹脂である、請求項1~5のいずれか1項に記載のパターン形成方法。
- 請求項1~6のいずれか1項に記載のパターン形成方法を含む、電子デバイスの製造方法。
- 樹脂Pと、活性光線又は放射線の照射により酸を発生する化合物とを含有し、
前記樹脂Pが、下記一般式(q1)で表される繰り返し単位Q1、及び、下記一般式(q2)で表される繰り返し単位Q2を有し、
前記樹脂Pの全繰り返し単位に対する、前記繰り返し単位Q2の含有量が、20モル%以上である、感活性光線性又は感放射線性樹脂組成物。
一般式(q1)中、R1は、水素原子又は炭素数1~20の有機基を表す。R2~R5は、それぞれ独立して、水素原子、フッ素原子、ヒドロキシ基又は炭素数1~20の有機基を表す。aは、1~6の整数を表す。但し、R2とR3、及びR4とR5は、互いに結合して、これらが結合している炭素原子と共に環員数3~10の環構造を形成していてもよい。
一般式(q2)中、R6は、水素原子又は炭素数1~20の有機基を表す。R7及びR8は、炭素数1~10の分岐構造を含んでよい鎖状のアルキル基を表す。R9は、炭素数1~10の分岐構造を含んでよいアルキル基又は炭素数3~14の単環式又は多環式のシクロアルキル基を表す。 - 前記一般式(q2)中、R9が、炭素数3~14の多環式シクロアルキル基を表す、請求項8に記載の感活性光線性又は感放射線性樹脂組成物。
- 前記樹脂Pが、更に、前記繰り返し単位Q1とは異なるラクトン構造を有する繰り返し単位を有する、請求項8又は9に記載の感活性光線性又は感放射線性樹脂組成物。
- 前記樹脂Pの全繰り返し単位に対する、前記繰り返し単位Q2の含有量が、40モル%以上である、請求項8~10のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物。
- 前記樹脂Pの全繰り返し単位に対する、前記繰り返し単位Q2の含有量が、50モル%以上である、請求項11に記載の感活性光線性又は感放射線性樹脂組成物。
- 前記樹脂Pが、前記繰り返し単位Q1と、前記繰り返し単位Q2と、前記繰り返し単位Q1とは異なるラクトン構造を有する繰り返し単位とのみからなる樹脂である、請求項8~12のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物。
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