WO2016208299A1 - 処理液及びパターン形成方法 - Google Patents
処理液及びパターン形成方法 Download PDFInfo
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- WO2016208299A1 WO2016208299A1 PCT/JP2016/064697 JP2016064697W WO2016208299A1 WO 2016208299 A1 WO2016208299 A1 WO 2016208299A1 JP 2016064697 W JP2016064697 W JP 2016064697W WO 2016208299 A1 WO2016208299 A1 WO 2016208299A1
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- acetate
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
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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
- G03F7/26—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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/34—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5022—Organic solvents containing oxygen
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5027—Hydrocarbons
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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
- G03F7/039—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
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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
- G03F7/039—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
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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
- G03F7/16—Coating processes; Apparatus therefor
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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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
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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
- G03F7/20—Exposure; Apparatus therefor
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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
- G03F7/20—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
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2037—Exposure with X-ray radiation or corpuscular radiation, through a mask with a pattern opaque to that radiation
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- 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
Definitions
- the present invention relates to a processing liquid for patterning a resist film and a pattern forming method. More specifically, the present invention is used in a semiconductor manufacturing process such as an IC (Integrated Circuit), a circuit board such as a liquid crystal and a thermal head, and a lithography process for other photofabrication.
- the present invention relates to a processing liquid and a pattern forming method.
- Patent Document 1 discloses using an organic processing liquid containing an ester solvent or a hydrocarbon solvent as an organic solvent as a developer or a rinsing liquid.
- the sulfur-containing compound derived from the raw material of the organic solvent interacts with the components contained in the resist pattern and remains on the resist pattern surface without volatilizing even after drying after the rinsing step, thereby causing foreign matter defects. Was estimated to occur.
- the present invention has been made in view of the above points, and an object of the present invention is to provide a processing liquid for patterning a resist film and a pattern forming method capable of suppressing the occurrence of defects in the resist pattern.
- the present inventor has found that a desired effect can be obtained by setting the content of the sulfur-containing compound contained in the treatment liquid to a specific amount or less. More specifically, the present inventors have found that the above object can be achieved by the following configuration.
- a resist film obtained from an actinic ray-sensitive or radiation-sensitive composition is used to perform at least one of development and washing, and is a processing liquid for resist film patterning containing an organic solvent, The processing liquid whose content of the compound containing a sulfur atom is 10 mmol / L or less in the said processing liquid.
- the processing solution according to (1) wherein the processing solution is a developer.
- the organic solvent contains an ester solvent.
- the ester solvent is at least selected from the group consisting of butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate and butyl butanoate.
- the processing liquid as described in said (3) containing any 1 type.
- the treatment step includes a rinsing step of washing with a rinsing liquid, The pattern formation according to (11) above, wherein the rinse liquid is the treatment liquid according to claim (1), (5), (6), (7), (8), (9) or (10) Method.
- the present invention it is possible to provide a processing liquid and a pattern forming method for resist film patterning that can suppress the occurrence of defects on the resist pattern surface.
- the processing liquid of the present invention is a processing liquid for resist film patterning, which is used to perform at least one of development and washing of a resist film obtained from an actinic ray-sensitive or radiation-sensitive composition, and contains an organic solvent. .
- the content of the sulfur-containing compound is 10 mmol / L or less. According to the treatment liquid of the present invention, it is possible to suppress the occurrence of resist pattern defects. Although the details of this reason have not yet been clarified, it is presumed as follows.
- the processing solution used as the developer and / or the rinsing solution has a low content of the sulfur-containing compound, the sulfur-containing compound contained in the processing solution and the component contained in the film after exposure (resist film).
- the reaction with the polar group in the polymer component can be suppressed.
- foreign substances generated on the surface of the resist pattern due to the reaction between the sulfur-containing compound and the polar group in the polymer component can be suppressed, so that it is presumed that the occurrence of defects in the resist pattern can be suppressed.
- the amount of the sulfur-containing compound is preferably further reduced in the treatment liquid used in a later process, that is, the treatment liquid of the present invention is preferably used as the rinse liquid.
- the content (concentration) of the sulfur-containing compound is 10 mmol / L or less, preferably 2.5 mmol / L or less, more preferably 1.0 mmol / L or less, Most preferably, it is not contained.
- the processing liquid is placed in a state where the stopper of the container (for example, the container described in JP-A-2014-112176) is closed, Even if it is used after being stored for 6 months at room temperature (23 ° C.), the occurrence of defects in the resist pattern can be suppressed.
- substantially does not contain means that it is not detected when the content (concentration) of the sulfur-containing compound is measured by a method that can be measured (for example, a measurement method described later) (below the detection limit value). Say something).
- the lower limit of the content (concentration) of the sulfur-containing compound is most preferably not substantially contained as described above.
- the content of the sulfur-containing compound may be 0.01 mmol / L or more.
- the sulfur-containing compound in the present invention is mainly an organic substance containing sulfur atoms originally contained as impurities in the components constituting the treatment liquid.
- sulfur-containing compounds with close boiling points such as benzothiophene and 3-methylbenzothiophene cannot be removed even after the petroleum fractional purification process. It tends to remain in trace amounts.
- Examples of the sulfur-containing compound contained in the treatment liquid include thiols, sulfides, and thiophenes. Among them, a sulfur compound having a boiling point of 190 ° C. or higher (particularly 220 ° C. or higher, more preferably 280 ° C. or higher) can be given.
- Specific examples of thiols include methanethiol, ethanethiol (ethyl mercaptan), 3-methyl-2-butene-1-thiol, 2-methyl-3-furanthiol, and furfurylthiol (furyl mercaptan).
- sulfides include dimethyl sulfide, dimethyl trisulfide, diisopropyl trisulfide, bis (2-methyl-3-furyl) disulfide, and the like.
- thiophenes include variously substituted alkylthiophenes, benzothiophenes, dibenzothiophenes, phenanthrothiophenes, benzonaphthothiophenes, thiophene sulfides, and the like.
- benzothiophenes for example, benzothiophene, 3-methylbenzothiophene, etc.
- the occurrence of resist pattern defects can be further suppressed.
- the content of the sulfur-containing compound in the treatment liquid of the present invention can be measured using, for example, a method defined in JIS K2541-6: 2013 “Sulfur content test method (ultraviolet fluorescence method)”.
- the present inventors When the compound further containing a phosphorus atom (hereinafter referred to as “phosphorus-containing compound”) is contained in the treatment liquid, the present inventors, like the above-described sulfur-containing compound, cause the phosphorus-containing compound to cause foreign matter defects. It came to know that it is easy to become. It is presumed that the phosphorus-containing compound interacts with the components contained in the resist pattern and remains on the resist pattern surface without being volatilized even after drying after the rinsing step. Therefore, in the treatment liquid of the present invention, the content of the compound containing a phosphorus atom is preferably 10 mmol / L or less, more preferably 5 mmol / L or less, and further preferably 2.5 mmol / L or less. Preferably, it is particularly preferably 1.0 mmol / L or less, and more preferably substantially free of a compound containing a phosphorus atom.
- substantially does not contain means that it is not detected when the content (concentration) of the phosphorus-containing compound is measured by a method that can be measured (for example, a measurement method described later) (below the detection limit value). Say something).
- a minimum of content (concentration) of a phosphorus containing compound it is most preferable not to contain substantially.
- the treatment such as distillation is excessively performed in order to reduce the content of the phosphorus-containing compound, the cost increases.
- the content of the phosphorus-containing compound may be 0.01 mmol / L or more.
- the phosphorus-containing compound is mainly an organic substance containing phosphorus atoms originally contained as impurities in the components constituting the treatment liquid, or an organic substance containing phosphorus atoms mixed during handling of the treatment liquid.
- examples thereof include phosphoric acid and phosphorus-based catalysts (organic phosphine, organic phosphine oxide) used for synthesizing organic solvents.
- the content of the compound containing phosphorus atoms in the treatment liquid of the present invention can be quantified by spectrophotometry as total phosphorus based on the method defined in JIS K0102: 2013.
- the content can be individually quantified using, for example, gas chromatography.
- the treatment liquid of the present invention can further reduce the content of sulfur-containing compounds and phosphorus-containing compounds by performing distillation or filtration of the organic solvent to be used.
- the processing solution of the present invention is usually used as a developing solution and / or a rinsing solution.
- the treatment liquid preferably contains an organic solvent, and further contains an antioxidant and / or a surfactant.
- the organic solvent contained in the processing solution, and the antioxidant and surfactant that may be contained will be described in detail in the description of the developer and rinse solution described later.
- the components contained in these and the components that can be contained will be described in detail in the order of developer and rinse solution.
- the developer which is a kind of the processing solution of the present invention, is used in a development step described later, and can be called an organic developer because it contains an organic solvent.
- the vapor pressure of the organic solvent (the vapor pressure as a whole in the case of a mixed solvent) 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 solvent is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
- the ester solvent is a solvent having an ester group in the molecule
- the ketone solvent is a solvent having a ketone group in the molecule
- the alcohol solvent is alcoholic in the molecule.
- It is a solvent having a hydroxyl group
- an amide solvent is a solvent having an amide group in the molecule
- an ether solvent is a solvent having an ether bond in the molecule.
- diethylene glycol monomethyl ether corresponds to both alcohol solvents and ether solvents in the above classification.
- a developer containing at least one kind of solvent selected from ketone solvents, ester solvents, alcohol solvents and ether solvents is preferable.
- ester solvent examples include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, propyl acetate, isopropyl acetate, amyl acetate (pentyl acetate), isoamyl acetate (isopentyl acetate, 3-methylbutyl acetate), acetic acid 2 -Methylbutyl, 1-methylbutyl acetate, hexyl acetate, isohexyl acetate, heptyl acetate, octyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), ethylene glycol mono Ethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol
- butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, and butyl butanoate are preferably used, and isoamyl acetate is particularly preferable. Preferably used.
- ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, Phenyl acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, ⁇ -butyrolactone, etc. Heptanone is preferred.
- alcohol solvents include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1 -Hexanol, 1-heptanol, 1-octanol, 1-decanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, 3-methyl-3-pen Tanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-2- Pentanol, 3-methyl-3-pentanol, 4-methyl- -Pentanol, 4-methyl-3-pentanol,
- ether solvents include glycol ether solvents that contain hydroxyl groups, glycol ether solvents that do not contain hydroxyl groups such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, anisole, and phenetole.
- aromatic ether solvents dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane, isopropyl ether and the like.
- an glycol ether solvent or an aromatic ether solvent such as anisole is used.
- amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
- hydrocarbon solvent examples include pentane, hexane, octane, nonane, decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, perfluoroheptane.
- Aliphatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, dipropylbenzene, etc.
- aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, dipropylbenzene, etc.
- aromatic hydrocarbon solvents such as the hydrocarbon solvent, an unsaturated hydrocarbon solvent can also be used, and examples thereof include unsaturated hydrocarbon solvents such as oc
- the number of double bonds and triple bonds of the unsaturated hydrocarbon solvent is not particularly limited, and the unsaturated hydrocarbon solvent may have any position in the hydrocarbon chain. Moreover, when an unsaturated hydrocarbon solvent has a double bond, cis body and trans body may be mixed.
- the aliphatic hydrocarbon solvent that is a hydrocarbon solvent may be a mixture of compounds having the same number of carbon atoms and different structures. For example, when decane is used as the aliphatic hydrocarbon solvent, 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isooctane, which are compounds having the same carbon number and different structures, are aliphatic hydrocarbon solvents. May be included.
- the compounds having the same number of carbon atoms and different structures may include only one kind or plural kinds as described above.
- the developer has 7 or more carbon atoms (preferably 7 to 14) from the standpoint that swelling of the resist film can be suppressed when EUV light (Extreme Ultra Violet) and EB (Electron Beam) are used in the exposure process described later. 7 to 12 are more preferable, and 7 to 10 are more preferable.) It is preferable to use an ester solvent having 2 or less heteroatoms.
- the hetero atom of the ester solvent is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom.
- the number of heteroatoms is preferably 2 or less.
- ester solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, Examples include heptyl propionate and butyl butanoate, and it is particularly preferable to use isoamyl acetate.
- the developer is replaced with the above ester solvent having 7 or more carbon atoms and 2 or less hetero atoms.
- a mixed solvent of the ester solvent and the hydrocarbon solvent or a mixed solvent of the ketone solvent and the hydrocarbon solvent may be used. Even in this case, it is effective in suppressing the swelling of the resist film.
- isoamyl acetate is preferably used as the ester solvent.
- the hydrocarbon solvent it is preferable to use a saturated hydrocarbon solvent (for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) from the viewpoint of adjusting the solubility of the resist film.
- a saturated hydrocarbon solvent for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.
- 2-heptanone is preferably used as the ketone solvent.
- a saturated hydrocarbon solvent for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.
- an unsaturated hydrocarbon solvent can be used as the hydrocarbon solvent.
- examples thereof include unsaturated hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, hexadecene and the like.
- the number of double bonds and triple bonds of the unsaturated hydrocarbon solvent is not particularly limited, and the unsaturated hydrocarbon solvent may have any position in the hydrocarbon chain.
- an unsaturated hydrocarbon solvent has a double bond, cis body and trans body may be mixed. In the case of using the above mixed solvent, the content of the hydrocarbon solvent depends on the solvent solubility of the resist film, and is not particularly limited.
- a plurality of the above organic solvents may be mixed, or may be used by mixing with other solvents 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.
- the concentration of the organic solvent (total in the case of a plurality of mixtures) in the developer is preferably 50% by mass or more, more preferably 50 to 100% by mass, still more preferably 85 to 90% by mass, and particularly preferably 95 to 100% by mass. %. Most preferably, it consists essentially of an organic solvent.
- the case where it consists only of an organic solvent includes the case where a trace amount surfactant, antioxidant, stabilizer, an antifoamer, etc. are contained.
- the organic solvent used as the developer include ester solvents.
- ester solvent it is more preferable to use a solvent represented by the general formula (S1) described later or a solvent represented by the general formula (S2) described later, and use a solvent represented by the general formula (S1). It is even more preferred that alkyl acetate be used, and butyl acetate, amyl acetate (pentyl acetate), and isoamyl acetate (isopentyl acetate) be most preferred.
- R and R ′ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group, or a halogen atom.
- R and R ′ may be bonded to each other to form a ring.
- the alkyl group, alkoxyl group, and alkoxycarbonyl group for R and R ′ preferably have 1 to 15 carbon atoms, and the cycloalkyl group preferably has 3 to 15 carbon atoms.
- R and R ′ are preferably a hydrogen atom or an alkyl group, and an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, and a ring formed by combining R and R ′ with respect to R and R ′, It may be substituted with a hydroxyl group, a group containing a carbonyl group (for example, acyl group, aldehyde group, alkoxycarbonyl, etc.), cyano group or the like.
- Examples of the solvent represented by the general formula (S1) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, and butyl lactate.
- examples thereof include isopropyl acid, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and the like.
- R and R ′ are unsubstituted alkyl groups.
- the solvent represented by the general formula (S1) is preferably alkyl acetate, more preferably butyl acetate, amyl acetate (pentyl acetate), or isoamyl acetate (isopentyl acetate), and is preferably isoamyl acetate. Further preferred.
- the solvent represented by the general formula (S1) may be used in combination with one or more other organic solvents.
- the combined solvent in this case is not particularly limited as long as it can be mixed without being separated into the solvent represented by the general formula (S1), and the solvents represented by the general formula (S1) may be used in combination.
- the solvent represented by the general formula (S1) may be used by mixing it with a solvent selected from other ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents and hydrocarbon solvents. Good.
- One or more solvents can be used in combination, but it is preferable to use one solvent in order to obtain stable performance.
- the mixing ratio of the solvent represented by the general formula (S1) and the combined solvent is usually 20:80 to 99: 1, preferably 50:50 to 97: by mass ratio. 3, more preferably 60:40 to 95: 5, and most preferably 60:40 to 90:10.
- a glycol ether solvent As the organic solvent used as the developer, a glycol ether solvent can be used.
- a glycol ether solvent a solvent represented by the following general formula (S2) may be used.
- R ′′ and R ′′ ′′ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a halogen atom.
- R ′′ and R ′′ ′′ may be bonded to each other to form a ring.
- R ′′ and R ′′ ′′ are preferably a hydrogen atom or an alkyl group.
- the carbon number of the alkyl group, alkoxyl group and alkoxycarbonyl group for R ′′ and R ′′ ′′ is preferably in the range of 1 to 15, and the carbon number of the cycloalkyl group is 3 to 15. Is preferred.
- R ′ ′′ represents an alkylene group or a cycloalkylene group.
- R ′ ′′ is preferably an alkylene group.
- the number of carbon atoms of the alkylene group for R ′ ′′ is preferably in the range of 1 to 10.
- the carbon number of the cycloalkylene group for R ′ ′′ is preferably in the range of 3 to 10.
- the ring formed by bonding to each other may be substituted with a hydroxyl group, a group containing a carbonyl group (for example, an acyl group, an aldehyde group, alkoxycarbonyl, etc.), a cyano group, or the like.
- the alkylene group for R ′ ′′ may have an ether bond in the alkylene chain.
- Examples of the solvent represented by the general formula (S2) include propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl.
- Ether acetate diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl-3-methoxy Propionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, ethyl methoxyacetate, ethyl ethoxyacetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4 -Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate
- R ′′ and R ′′ ′′ are preferably unsubstituted alkyl groups
- R ′ ′′ is preferably an unsubstituted alkylene group
- R ′′ and R ′′ ′′ are methyl groups.
- R ′′ and R ′′ ′′ are more preferably methyl groups.
- the solvent represented by the general formula (S2) may be used in combination with one or more other organic solvents.
- the combined solvent in this case is not particularly limited as long as it can be mixed without being separated into the solvent represented by the general formula (S2), and the solvents represented by the general formula (S2) may be used in combination.
- the solvent represented by the general formula (S2) may be used by mixing it with a solvent selected from other ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents and hydrocarbon solvents. Good.
- One or more solvents can be used in combination, but it is preferable to use one solvent in order to obtain stable performance.
- the mixing ratio of the solvent represented by formula (S2) and the combination solvent is usually 20:80 to 99: 1, preferably 50:50 to 97: by mass. 3, more preferably 60:40 to 95: 5, and most preferably 60:40 to 90:10.
- an ether type solvent can also be mentioned suitably.
- the ether solvent that can be used include the ether solvents described above, and among these, an ether solvent containing one or more aromatic rings is preferable, and a solvent represented by the following general formula (S3) is more preferable. Most preferred is anisole.
- R S represents an alkyl group.
- the alkyl group preferably has 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and most preferably a methyl group.
- organic solvent contained in the developer of the present invention an organic solvent used in an actinic ray-sensitive or radiation-sensitive composition described later can be used.
- the developer preferably contains a surfactant. Thereby, the wettability with respect to the resist film is improved, and the development proceeds more effectively.
- the surfactant the same surfactants as those used in the actinic ray-sensitive or radiation-sensitive composition described later can be used.
- the content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total mass of the developer. .
- the developer preferably contains an antioxidant. Thereby, generation
- amine-based antioxidants and phenol-based antioxidants are preferably used.
- amine antioxidants include 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine, and phenyl-2.
- Naphthylamine antioxidants such as naphthylamine; N, N′-diisopropyl-p-phenylenediamine, N, N′-diisobutyl-p-phenylenediamine, N, N′-diphenyl-p-phenylenediamine, N, N ′ -Di- ⁇ -naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N '-Phenyl-p-phenylenediamine, dioctyl-p-phenyle Phenylenediamine antioxidants such as diamine, phenylhexyl-p-phenylenediamine, phenyloctyl-p-phenylenediamine; dipyridy
- phenolic antioxidant examples include 2,6-di-tert-butylphenol (hereinafter, tertiary butyl is abbreviated as t-butyl), 2,6-di-t-butyl-p-cresol.
- the content of the antioxidant is not particularly limited, but is preferably 0.0001 to 1% by mass, more preferably 0.0001 to 0.1% by mass, and 0.0001 to 0% with respect to the total mass of the developer. More preferred is 0.01 mass%. When it is 0.0001% by mass or more, a more excellent antioxidant effect is obtained, and when it is 1% by mass or less, development residue tends to be suppressed.
- the developer of the present invention preferably contains a basic compound.
- the basic compound include compounds exemplified as the basic compound (E) that can be contained in the actinic ray-sensitive or radiation-sensitive composition described later.
- the basic compounds that can be contained in the developer of the present invention the following nitrogen-containing compounds can be preferably used.
- the nitrogen-containing compound When the nitrogen-containing compound is contained in the developer, the nitrogen-containing compound interacts with a polar group generated in the resist film by the action of an acid, and can further improve the insolubility of the exposed portion with respect to the organic solvent.
- the interaction between the nitrogen-containing compound and the polar group includes an action of reacting the nitrogen-containing compound and the polar group to form a salt, an action of forming an ionic bond, and the like.
- the compound represented by Formula (1) is preferable.
- R 1 and R 2 each independently represent a hydrogen atom, a hydroxyl group, a formyl group, an alkoxy group, an alkoxycarbonyl group, a chain hydrocarbon group having 1 to 30 carbon atoms, or 3 to 3 carbon atoms.
- R 3 represents a hydrogen atom, a hydroxyl group, a formyl group, an alkoxy group, an alkoxycarbonyl group, an n-valent chain hydrocarbon group having 1 to 30 carbon atoms, an n-valent alicyclic hydrocarbon group having 3 to 30 carbon atoms, It is an n-valent aromatic hydrocarbon group having 6 to 14 carbon atoms or a combination of two or more of these groups.
- n is an integer of 1 or more. However, when n is 2 or more, the plurality of R 1 and R 2 may be the same or different. Further, any two of R 1 to R 3 may be bonded to form a ring structure together with the nitrogen atom to which each is bonded.
- Examples of the chain hydrocarbon group having 1 to 30 carbon atoms represented by R 1 and R 2 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methylpropyl. Group, 1-methylpropyl group, t-butyl group and the like.
- Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms represented by R 1 and R 2 include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a norbornyl group.
- Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R 1 and R 2 include a phenyl group, a tolyl group, and a naphthyl group.
- Examples of the group formed by combining two or more of these groups represented by R 1 and R 2 include aralkyl groups having 6 to 12 carbon atoms such as benzyl, phenethyl, naphthylmethyl, and naphthylethyl groups. Can be mentioned.
- Examples of the n-valent chain hydrocarbon group having 1 to 30 carbon atoms represented by R 3 include groups exemplified as the chain hydrocarbon group having 1 to 30 carbon atoms represented by R 1 and R 2 above. And a group obtained by removing (n-1) hydrogen atoms from the same group.
- Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms represented by R 3 include the same groups as those exemplified as the cyclic hydrocarbon group having 3 to 30 carbon atoms represented by R 1 and R 2. And a group obtained by removing (n-1) hydrogen atoms from the group.
- Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R 3 are the same as those exemplified as the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R 1 and R 2 . And a group obtained by removing (n-1) hydrogen atoms from the group.
- the group formed by combining two or more of these groups represented by R 3 is the same as the group exemplified as a group formed by combining two or more of these groups represented by R 1 and R 2 . And a group obtained by removing (n-1) hydrogen atoms from the group.
- the groups represented by R 1 to R 3 may be substituted.
- the substituent include a methyl group, an ethyl group, a provir group, an n-butyl group, a t-butyl group, a hydroxyl group, a carboxy group, a halogen atom, and an alkoxy group.
- the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
- alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
- Examples of the compound represented by the above formula (1) include (cyclo) alkylamine compounds, nitrogen-containing heterocyclic compounds, amide group-containing compounds, urea compounds and the like.
- Examples of (cyclo) alkylamine compounds include compounds having one nitrogen atom, compounds having two nitrogen atoms, compounds having three or more nitrogen atoms, and the like.
- Examples of (cyclo) alkylamine compounds having one nitrogen atom include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, 1-aminodecane, cyclohexylamine and the like.
- Di (cyclo) alkylamines such as dicyclohexylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri -N-octylamine, tri-n-nonylamine, tri Tri (cyclo) alkylamines such as n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, tricyclohexylamine; substituted alkylamines such as triethanolamine; aniline, N-methylaniline,
- Examples of the (cyclo) alkylamine compound having two nitrogen atoms include ethylenediamine, tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, and 4,4 ′.
- Examples of the (cyclo) alkylamine compound having 3 or more nitrogen atoms include polymers such as polyethyleneimine, polyallylamine and 2-dimethylaminoethylacrylamide.
- nitrogen-containing heterocyclic compounds include nitrogen-containing aromatic heterocyclic compounds and nitrogen-containing aliphatic heterocyclic compounds.
- nitrogen-containing aromatic heterocyclic compound examples include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2.
- -Imidazoles such as methyl-1H-imidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenyl Examples thereof include pyridines such as pyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, and 2,2 ′: 6 ′, 2 ′′ -terpyridine.
- nitrogen-containing aliphatic heterocyclic compound examples include piperazine such as piperazine and 1- (2-hydroxyethyl) piperazine; pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, proline, piperidine, piperidine ethanol, 3-piperidino- 1,2-propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, 3- (N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane and the like.
- piperazine such as piperazine and 1- (2-hydroxyethyl) piperazine
- pyrazine pyrazole, pyridazine, quinosaline
- purine pyrrolidine, proline
- piperidine piperidine ethanol
- Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, and Nt-butoxy.
- urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, and 1,3-diphenylurea.
- nitrogen-containing compounds having an SP value of 18 or less are preferably used from the viewpoint of suppressing development defects. This is because a nitrogen-containing compound having an SP value of 18 or less has good affinity with a rinsing liquid used in a rinsing process described later, and can suppress development defects such as precipitation.
- (Cyclo) alkylamine compounds and nitrogen-containing aliphatic heterocyclic compounds satisfying the above conditions are preferred, and 1-aminodecane, di-n-octylamine, tri-n-octylamine, and tetramethylethylenediamine are preferred. More preferred.
- the following table shows the SP values and the like of these nitrogen-containing aliphatic heterocyclic compounds.
- the content of the basic compound (preferably a nitrogen-containing compound) in the developer is not particularly limited, but is preferably 10% by mass or less, based on the total amount of the developer, in that the effect of the present invention is more excellent. 5 to 5% by mass is preferable.
- the above nitrogen-containing compounds may be used alone or in combination of two or more having different chemical structures.
- the rinsing liquid which is a kind of the processing liquid of the present invention is used in a rinsing step which will be described later, and can also be called an organic rinsing liquid because it contains an organic solvent.
- This rinse solution is used for “cleaning” of the resist film (that is, “rinsing” of the resist film) using the treatment liquid of the present invention.
- the vapor pressure of the rinsing liquid (the vapor pressure as a whole in the case of a mixed 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, and 0.12 kPa or more at 20 ° C. Most preferably, it is 3 kPa or less.
- Organic solvent Various organic solvents are used as the organic solvent contained in the rinsing liquid of the present invention. From the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. It is preferable to use at least one organic solvent selected. Specific examples of these organic solvents are the same as those described for the developer.
- organic solvent contained in the rinsing liquid in the case where EUV light (Extreme Ultra Violet) or EB (Electron Beam) is used in an exposure process described later, it is preferable to use a hydrocarbon solvent among the above organic solvents. More preferably, an aromatic hydrocarbon solvent is used.
- an aliphatic hydrocarbon solvent having 5 or more carbon atoms for example, pentane, hexane, octane, decane, undecane, dodecane, Hexadecane, etc.
- aliphatic hydrocarbon solvents having 8 or more carbon atoms are preferred
- aliphatic hydrocarbon solvents having 10 or more carbon atoms are more preferred.
- the upper limit of the carbon atom number of the said aliphatic hydrocarbon solvent is not specifically limited, For example, 16 or less is mentioned, 14 or less is preferable and 12 or less is more preferable.
- an unsaturated hydrocarbon solvent can also be used as the hydrocarbon solvent contained in the rinse liquid, and examples thereof include unsaturated hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, hexadecene and the like.
- the number of double bonds and triple bonds of the unsaturated hydrocarbon solvent is not particularly limited, and the unsaturated hydrocarbon solvent may have any position in the hydrocarbon chain.
- an unsaturated hydrocarbon solvent has a double bond, cis body and trans body may be mixed.
- the developer slightly soaked into the resist film after development is washed away, and swelling is further suppressed. Thus, the effect of suppressing pattern collapse is further exhibited.
- a hydrocarbon solvent especially an aliphatic hydrocarbon solvent
- the mixed solvent of the said ester solvent and the said hydrocarbon solvent or the mixed solvent of the said ketone solvent and the said hydrocarbon solvent as an organic solvent contained in a rinse liquid.
- a hydrocarbon solvent as a main component.
- an ester solvent and a hydrocarbon solvent are used in combination, it is preferable to use butyl acetate or isoamyl acetate as the ester solvent.
- the hydrocarbon solvent it is preferable to use a saturated hydrocarbon solvent (for example, decane, dodecane, undecane, hexadecane, etc.) from the viewpoint that the above effect is further exhibited.
- 2-heptanone is preferably used as the ketone solvent.
- the hydrocarbon solvent it is preferable to use a saturated hydrocarbon solvent (for example, decane, dodecane, undecane, hexadecane, etc.) from the viewpoint that the above effect is further exhibited.
- an ester solvent and a hydrocarbon solvent are used in combination, or when a ketone solvent and a hydrocarbon solvent are used in combination, an unsaturated hydrocarbon solvent can be used as the hydrocarbon solvent.
- Examples thereof include unsaturated hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, hexadecene and the like.
- the number of double bonds and triple bonds of the unsaturated hydrocarbon solvent is not particularly limited, and the unsaturated hydrocarbon solvent may have any position in the hydrocarbon chain.
- an unsaturated hydrocarbon solvent has a double bond, cis body and trans body may be mixed.
- the organic solvent contained in the rinse liquid is an embodiment in which at least one selected from the group consisting of the ester solvent and the ketone solvent is used from the viewpoint of being particularly effective for reducing residues after development. May be.
- the rinsing liquid contains at least one selected from the group consisting of ester solvents and ketone solvents, butyl acetate, isopentyl acetate (isoamyl acetate), n-pentyl acetate, ethyl 3-ethoxypropionate (EEP, Ethyl-3-ethoxypropionate) and at least one solvent selected from the group consisting of 2-heptanone as a main component, preferably at least selected from the group consisting of butyl acetate and 2-heptanone It is particularly preferable to contain one solvent as a main component.
- the rinse liquid is selected from the group consisting of ester solvents, glycol ether solvents, ketone solvents, alcohol solvents. It is preferable that propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl acetate, ethyl lactate, methyl 3-methoxypropionate, cyclohexanone, methyl ethyl ketone, ⁇ - A solvent selected from the group consisting of butyrolactone, propanol, 3-methoxy-1-butanol, N-methylpyrrolidone and propylene carbonate is preferred.
- PMEA propylene glycol monomethyl ether acetate
- PGME propylene glycol monomethyl ether
- ethyl acetate propylene glycol monomethyl ether
- ethyl lactate ethyl acetate
- ethyl lactate ethyl acetate
- an ester solvent when used as the organic solvent, it is preferable to use two or more ester solvents from the viewpoint that the above effect is further exhibited.
- an ester solvent preferably butyl acetate
- an ester solvent preferably propylene glycol monomethyl ether acetate (PGMEA)
- PMEA propylene glycol monomethyl ether acetate
- a glycol ether solvent may be used in addition to the ester solvent (one type or two or more types) from the viewpoint that the above effect is further exhibited.
- Specific examples in this case include using an ester solvent (preferably butyl acetate) as a main component and a glycol ether solvent (preferably propylene glycol monomethyl ether (PGME)) as a subcomponent.
- a glycol ether solvent preferably propylene glycol monomethyl ether (PGME)
- PGME propylene glycol monomethyl ether
- an ester solvent and / or a glycol ether solvent is used in addition to the ketone solvent (one or two or more) from the viewpoint that the above effects are further exhibited. May be.
- Specific examples in this case include a ketone solvent (preferably 2-heptanone) as a main component, an ester solvent (preferably propylene glycol monomethyl ether acetate (PGMEA)) and / or a glycol ether solvent (preferably propylene).
- Glycol monomethyl ether (PGME) is used as an accessory component.
- the above “main component” means that the content of the organic solvent is 50 to 100% by mass, preferably 70 to 100% by mass, more preferably 80 to 100% by mass, More preferably, it is 90 to 100% by mass, and particularly preferably 95 to 100% by mass.
- the content of the auxiliary component is preferably 0.1 to 20% by mass with respect to the total mass (100% by mass) of the main component, and preferably 0.5 to 10%. More preferably, it is more preferably 1 to 5% by weight.
- a plurality of organic solvents may be mixed, or may be used by mixing with an organic solvent other than the above.
- the solvent may be mixed with water, but the water content in the rinsing liquid is usually 60% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less. is there.
- a favorable rinse characteristic can be acquired by making a moisture content into 60 mass% or less.
- the rinse liquid contains a surfactant.
- a surfactant the same surfactants as those used in the actinic ray-sensitive or radiation-sensitive composition described later can be used.
- the content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total mass of the rinse liquid. .
- the rinse liquid preferably contains an antioxidant. Thereby, generation
- Specific examples and contents of the antioxidant are as described in the above developer.
- non-chemical amplification resists include the following.
- Resist materials whose solubility changes when the main chain is cleaved by irradiation with g-line, h-line, i-line, KrF, ArF, EB, EUV or the like, and the molecular weight is lowered (for example, JP 2013-210411 A)
- the main component is a copolymer of an ⁇ -chloroacrylate ester compound and an ⁇ -methylstyrene compound described in paragraphs 0025 to 0029 and 0056 of the publication and paragraphs 0032 to 0036 and 0063 of US Patent Publication 2015/0008211.
- Resist materials (2) Resist materials such as hydrogen silsesquioxane (HSQ) accompanied by silanol condensation reaction caused by g-line, h-line, i-line, KrF, ArF, EB, EUV, etc., chlorine-substituted calixarene, etc.
- HQ hydrogen silsesquioxane
- the developer and the rinsing liquid described above can be suitably applied to a silicon-based resist.
- the silicon resist include resist materials described in paragraphs 0010 to 0062 and paragraphs 0129 to 0165 described in JP-A-2008-83384.
- the pattern forming method of the present invention includes a resist film forming step of forming a resist film using an actinic ray-sensitive or radiation-sensitive composition (hereinafter also referred to as “resist composition”), and an exposure step of exposing the resist film. And a treatment step of treating the exposed resist film with the treatment liquid described above (a treatment liquid having a sulfur-containing compound content of 10 mmol / L or less).
- the treatment liquid described above a treatment liquid having a sulfur-containing compound content of 10 mmol / L or less.
- the resist film forming step is a step of forming a resist film using an actinic ray-sensitive or radiation-sensitive composition, and can be performed, for example, by the following method.
- a resist film actinic ray-sensitive or radiation-sensitive composition film
- each component described later is dissolved in a solvent and activated.
- a light-sensitive or radiation-sensitive composition is prepared, filtered as necessary, and then applied onto a substrate.
- the filter is preferably made of polytetrafluoroethylene, polyethylene or nylon having a pore size of 0.1 microns or less, more preferably 0.05 microns or less, and still more preferably 0.03 microns or less.
- the actinic ray-sensitive or radiation-sensitive composition is applied to a substrate (eg, silicon or silicon dioxide coating) used for manufacturing an integrated circuit element by an appropriate application method such as a spinner. Thereafter, it is dried to form a resist film. If necessary, various base films (inorganic films, organic films, antireflection films) may be formed under the resist film.
- a substrate eg, silicon or silicon dioxide coating
- an appropriate application method such as a spinner.
- Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
- the heating temperature is preferably 80 to 150 ° C., more preferably 80 to 140 ° C., and still more preferably 80 to 130 ° C.
- the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.
- the film thickness of the resist film is generally 200 nm or less, preferably 100 nm or less.
- the thickness of the formed resist film is preferably 50 nm or less. If the film thickness is 50 nm or less, pattern collapse is less likely to occur when a development process described later is applied, and better resolution performance is obtained. More preferably, the film thickness ranges from 15 nm to 45 nm. If the film thickness is 15 nm or more, sufficient etching resistance can be obtained. More preferably, the film thickness ranges from 15 nm to 40 nm. When the film thickness is within this range, etching resistance and better resolution performance can be satisfied at the same time.
- a top coat may be formed on the upper layer of the resist film. It is preferable that the top coat is not mixed with the resist film and can be uniformly applied to the upper layer of the resist film.
- the topcoat is not particularly limited, and a conventionally known topcoat can be formed by a conventionally known method. For example, the topcoat can be formed based on the description in paragraphs 0072 to 0082 of JP-A No. 2014-059543.
- the top coat preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond and an ester bond.
- An exposure process is a process of exposing the said resist film, for example, can be performed with the following method.
- the resist film formed as described above is irradiated with actinic rays or radiation through a predetermined mask. Note that in electron beam irradiation, drawing (direct drawing) without using a mask is common. Although it does not specifically limit as actinic light or a radiation, For example, they are a KrF excimer laser, an ArF excimer laser, EUV light (Extreme Ultra Violet), an electron beam (EB, Electron Beam), etc.
- the exposure may be immersion exposure.
- baking is preferably performed after exposure and before development.
- the reaction of the exposed part is promoted by baking, and the sensitivity and pattern shape become better.
- the heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C, and still more preferably 80 to 130 ° C.
- the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds. Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
- the development step is a step of developing the exposed resist film with a developer.
- 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.
- dip method a method in which a substrate is immersed in a tank filled with a developer for a certain period of time
- paddle 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
- spray method a method of spraying the developer on the substrate surface
- the development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is usually 10 to 300 seconds, preferably 20 to 120 seconds.
- the temperature of the developer is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.
- the developer used in the developing step it is preferable to use the above-described processing solution.
- the developer is as described above.
- development with an alkaline developer may be performed (so-called double development).
- the rinsing step is a step of washing (rinsing) with a rinsing liquid after the developing step.
- the developed wafer is cleaned using the rinsing liquid.
- the method of the cleaning process is not particularly limited. For example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (rotary discharge 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), and the like can be applied.
- a cleaning process is performed by a rotary discharge method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.
- the rinsing time is not particularly limited, but is usually 10 to 300 seconds.
- the time is preferably 10 seconds to 180 seconds, and most preferably 20 seconds to 120 seconds.
- the temperature of the rinse liquid is preferably 0 to 50 ° C., more preferably 15 to 35 ° C.
- a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.
- a heat treatment can be performed in order to remove the solvent remaining in the pattern.
- the heating temperature is not particularly limited as long as a good resist pattern can be obtained, and is usually 40 to 160 ° C.
- the heating temperature is preferably 50 to 150 ° C, and most preferably 50 to 110 ° C.
- the heating time is not particularly limited as long as a good resist pattern can be obtained, but it is usually 15 to 300 seconds, and preferably 15 to 180 seconds.
- the rinse liquid it is preferable to use the above-described treatment liquid.
- the explanation of the rinse liquid is as described above.
- At least one of the developing solution and the rinsing solution is the processing solution described above, but it is preferable that both of them are the processing solutions described above.
- the developer and the rinse liquid are stored in a waste liquid tank through a pipe after use.
- a hydrocarbon solvent is used as the rinsing liquid
- the resist dissolved in the developer is deposited and adheres to the wafer side rear surface, the piping side surface, and the like, and the apparatus is soiled.
- the solvent in which the resist is dissolved is again passed through the pipe.
- a method of passing through the piping after cleaning with a rinsing liquid, cleaning the back and side surfaces of the substrate with a solvent that dissolves the resist, or passing the solvent through which the resist dissolves without contacting the resist. The method of flowing is mentioned.
- the solvent to be passed through the pipe is not particularly limited as long as it can dissolve the resist, and examples thereof include the organic solvents described above, such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl.
- PGMEA propylene glycol monomethyl ether acetate
- PGMEA propylene glycol monoethyl ether acetate
- propylene glycol monopropyl propylene glycol monopropyl.
- Ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol mono Ethyl ether, propylene glycol monopropyl ether, propylene Glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, acetone, or the like can be used.
- PGMEA, PGME, and cyclohexanone can be preferably used.
- the actinic ray-sensitive or radiation-sensitive composition preferably used in combination with the treatment liquid of the present invention preferably contains a resin (A).
- the resin (A) is at least (i) a repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group (may further have a repeating unit having a phenolic hydroxyl group), or at least (ii) It has a repeating unit having a phenolic hydroxyl group.
- Examples of the repeating unit having a phenolic hydroxyl group contained in the resin (A) include a repeating unit represented by the following general formula (I).
- R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- R 42 may form a ring with Ar 4, R 42 in this case represents a single bond or an alkylene group.
- X 4 represents a single bond, —COO—, or —CONR 64 —, and R 64 represents a hydrogen atom or an alkyl group.
- L 4 represents a single bond or an alkylene group.
- Ar 4 represents an (n + 1) -valent aromatic ring group, and when bonded to R 42 to form a ring, represents an (n + 2) -valent aromatic ring group.
- n represents an integer of 1 to 5.
- the alkyl group represented by R 41 , R 42 and R 43 in the general formula (I) is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec- Examples thereof include alkyl groups having 20 or less carbon atoms such as butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl groups having 8 or less carbon atoms, particularly preferably alkyl groups having 3 or less carbon atoms. Can be mentioned.
- the cycloalkyl group represented by R 41 , R 42 and R 43 in the general formula (I) may be monocyclic or polycyclic. Preferred examples include a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.
- Examples of the halogen atom of R 41 , R 42 and R 43 in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
- the alkyl group contained in the alkoxycarbonyl group of R 41 , R 42 and R 43 in the general formula (I) the same alkyl groups as those described above for R 41 , R 42 and R 43 are preferable.
- Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls. Groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, nitro groups and the like, and the substituent preferably has 8 or less carbon atoms.
- Ar 4 represents an (n + 1) -valent aromatic ring group.
- the divalent aromatic ring group in the case where n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, an anthracenylene group, or the like.
- Examples of preferred aromatic ring groups include heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole.
- n + 1) -valent aromatic ring group in the case where n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic ring group.
- the group formed can be preferably mentioned.
- the (n + 1) -valent aromatic ring group may further have a substituent.
- Examples of the substituent that the above-described alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n + 1) -valent aromatic ring group may have include R 41 , R 42 , and R 43 in formula (I).
- Examples include alkyl groups such as alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, and butoxy groups; aryl groups such as phenyl groups; and the like.
- R 64 represents a hydrogen atom, an alkyl group
- the alkyl group for R 64 in, preferably an optionally substituted methyl group, an ethyl group, a propyl group , An isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a dodecyl group, and the like, and an alkyl group having a carbon number of 8 or less is more preferable.
- X 4 is preferably a single bond, —COO— or —CONH—, and more preferably a single bond or —COO—.
- the alkylene group for L 4 is preferably an alkylene group having 1 to 8 carbon atoms such as an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group.
- Ar 4 an optionally substituted aromatic ring group having 6 to 18 carbon atoms is more preferable, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are particularly preferable.
- the repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure. That is, Ar 4 is preferably a benzene ring group.
- Preferred examples of the repeating unit having a phenolic hydroxyl group that the resin (A) has include a repeating unit represented by the following general formula (p1).
- R represents a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different. As R in the general formula (p1), a hydrogen atom is particularly preferable.
- Ar in the general formula (p1) represents an aromatic ring, for example, an aromatic carbon which may have a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a phenanthrene ring.
- a hydrogen ring or a heterocycle such as a thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring, etc.
- aromatic ring heterocycles is especially, a benzene ring is most preferable.
- M in the general formula (p1) represents an integer of 1 to 5, preferably 1.
- the content of the repeating unit having a phenolic hydroxyl group is preferably from 0 to 50 mol%, more preferably from 0 to 45 mol%, still more preferably from 0 to 40 mol%, based on all repeating units in the resin (A). is there.
- the repeating unit having a group that decomposes by the action of an acid and generates a carboxyl group in the resin (A) is a repeating unit having a group in which a hydrogen atom of the carboxyl group is substituted with a group that decomposes and leaves by the action of an acid It is.
- R 36 to R 39 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- R 36 and R 37 may be bonded to each other to form a ring.
- R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- the repeating unit represented by the following general formula (AI) is preferable as the repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group.
- Xa 1 represents a hydrogen atom or an alkyl group which may have a substituent.
- T represents a single bond or a divalent linking group.
- Rx 1 to Rx 3 each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl groups. Two of Rx 1 to Rx 3 may combine to form a cycloalkyl group (monocyclic or polycyclic).
- Examples of the optionally substituted alkyl group represented by Xa 1 include a methyl group or a group represented by —CH 2 —R 11 .
- R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. And more preferably a methyl group.
- Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group, or the like.
- Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like.
- Rt represents an alkylene group or a cycloalkylene group.
- T is preferably a single bond or a —COO—Rt— group.
- Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH 2 — group, — (CH 2 ) 2 — group, or — (CH 2 ) 3 — group.
- the alkyl group of Rx 1 to Rx 3 is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.
- Examples of the cycloalkyl group of Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group.
- Examples of the cycloalkyl group formed by combining two of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group
- a monocyclic cycloalkyl group such as a group is preferred.
- a monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.
- the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. It may be replaced.
- the repeating unit represented by the general formula (AI) preferably has, for example, an embodiment in which Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the above-described cycloalkyl group.
- Each of the above groups may have a substituent.
- substituents include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, an alkoxy group.
- substituents include carbonyl groups (having 2 to 6 carbon atoms), and those having 8 or less carbon atoms are preferred.
- the repeating unit represented by formula (AI) is preferably an acid-decomposable (meth) acrylic acid tertiary alkyl ester-based repeating unit (Xa 1 represents a hydrogen atom or a methyl group, and T is a single bond. Is a repeating unit). More preferably, Rx 1 to Rx 3 are each independently a repeating unit representing a linear or branched alkyl group, and more preferably, Rx 1 to Rx 3 are each independently a repeating unit representing a linear alkyl group. Unit.
- Rx and Xa 1 represent a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
- Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms.
- Z represents a substituent containing a polar group, and when there are a plurality of them, each is independent.
- p represents 0 or a positive integer.
- Examples of the substituent containing a polar group represented by Z include a linear or branched alkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamide group, or a sulfonamide group, and a cycloalkyl group. Is an alkyl group having a hydroxyl group. As the branched alkyl group, an isopropyl group is particularly preferable.
- the content of the repeating unit having a group capable of decomposing by the action of an acid to generate a carboxyl group is preferably 20 to 90 mol%, more preferably 25 to 80 mol%, based on all repeating units in the resin (A). More preferably, it is 30 to 70 mol%.
- the resin (A) preferably further contains a repeating unit having a lactone group.
- the lactone group any group can be used as long as it contains a lactone structure, but a group containing a 5- to 7-membered ring lactone structure is preferred, and a bicyclo structure is added to the 5- to 7-membered ring lactone structure, Those in which other ring structures are condensed to form a spiro structure are preferred. It is more preferable to have a repeating unit having a group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-16). Further, a group having a lactone structure may be directly bonded to the main chain.
- Preferred lactone structures are groups represented by general formulas (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14).
- the lactone structure moiety may or may not have a substituent (Rb 2 ).
- Preferred substituents (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like.
- n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb 2 may be the same or different, and a plurality of Rb 2 may be bonded to form a ring.
- Examples of the repeating unit having a group having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-16) include a repeating unit represented by the following general formula (AI). Can do.
- Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group represented by Rb 0 may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb 0 is preferably a hydrogen atom or a methyl group.
- Ab is a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these.
- Preferred is a single bond or a linking group represented by —Ab 1 —CO 2 —.
- Ab 1 is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.
- V represents a group represented by any one of the general formulas (LC1-1) to (LC1-16).
- the repeating unit having a group having a lactone structure usually has an optical isomer, but any optical isomer may be used.
- One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used.
- the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.
- repeating unit having a group having a lactone structure examples include:
- the content of the repeating unit having a lactone group is preferably from 1 to 30 mol%, more preferably from 5 to 25 mol%, still more preferably from 5 to 20 mol%, based on all repeating units in the resin (A). .
- the resin (A) can further have a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. This improves the substrate adhesion and developer compatibility.
- the alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group, a diamantyl group, or a norbornane group.
- the polar group is preferably a hydroxyl group or a cyano group. Specific examples of the repeating unit having a polar group are listed below, but the present invention is not limited thereto.
- the content thereof is preferably 1 to 30 mol%, more preferably 5%, based on all repeating units in the resin (A). It is ⁇ 25 mol%, more preferably 5 to 20 mol%.
- a repeating unit having a group capable of generating an acid (photoacid generating group) upon irradiation with actinic rays or radiation can be included.
- the repeating unit having this photoacid-generating group corresponds to the compound (B) that generates an acid upon irradiation with actinic rays or radiation described later.
- Examples of such a repeating unit include a repeating unit represented by the following general formula (4).
- R 41 represents a hydrogen atom or a methyl group.
- L 41 represents a single bond or a divalent linking group.
- L 42 represents a divalent linking group.
- W represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.
- examples of the repeating unit represented by the general formula (4) include the repeating units described in paragraphs ⁇ 0094> to ⁇ 0105> of JP-A No. 2014-041327.
- the content of the repeating unit having a photoacid-generating group is preferably 1 to 40 mol% with respect to all the repeating units in the resin (A). More preferably, it is 5 to 35 mol%, and still more preferably 5 to 30 mol%.
- Resin (A) 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 a solvent that dissolves an actinic ray-sensitive or radiation-sensitive composition such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone. More preferably, the polymerization is performed using the same solvent as that used in the actinic ray-sensitive or radiation-sensitive composition. 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 preferable.
- Preferable 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.
- 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.
- Purification can be accomplished by using a liquid-liquid extraction method that removes residual monomers and oligomer components by washing with water or an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less.
- the weight average molecular weight of the resin (A) is preferably from 1,000 to 200,000, more preferably from 3,000 to 20,000, most preferably from 5,000 to 15, as a polystyrene converted value by the GPC method. 000.
- the weight average molecular weight is preferably from 1,000 to 200,000, more preferably from 3,000 to 20,000, most preferably from 5,000 to 15, as a polystyrene converted value by the GPC method. 000.
- Another particularly preferable form of the weight average molecular weight of the resin (A) is 3,000 to 9,500 in terms of polystyrene by GPC method.
- the degree of dispersion is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. . The smaller the degree of dispersion, the better the resolution and the resist shape, the smoother the side wall of the resist pattern, and the better the roughness.
- the content of the resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass in the total solid content.
- the resin (A) may be used alone or in combination.
- the resin (A) may contain a repeating unit represented by the following general formula (VI) as the repeating unit (a).
- R 61 , R 62 and R 63 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- R 62 may be bonded to Ar 6 to form a ring, and R 62 in this case represents a single bond or an alkylene group.
- X 6 represents a single bond, —COO—, or —CONR 64 —.
- R 64 represents a hydrogen atom or an alkyl group.
- L 6 represents a single bond or an alkylene group.
- Ar 6 represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when bonded to R 62 to form a ring.
- Y 2 independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ⁇ 2. However, at least one of Y 2 represents a group capable of leaving by the action of an acid.
- n represents an integer of 1 to 4.
- a structure represented by the following general formula (VI-A) is more preferable.
- L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
- M represents a single bond or a divalent linking group.
- Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group. At least two of Q, M, and L 1 may combine to form a ring (preferably a 5-membered or 6-membered ring).
- the repeating unit represented by the general formula (VI) is preferably a repeating unit represented by the following general formula (3).
- Ar 3 represents an aromatic ring group.
- R 3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
- M 3 represents a single bond or a divalent linking group.
- Q 3 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. At least two of Q 3 , M 3 and R 3 may be bonded to form a ring.
- the aromatic ring group represented by Ar 3 is the same as Ar 6 in the general formula (VI) when n in the general formula (VI) is 1, more preferably a phenylene group or a naphthylene group, A phenylene group is preferred.
- repeating unit represented by the general formula (VI) Specific examples of the repeating unit represented by the general formula (VI) are shown below as preferred specific examples of the repeating unit (a), but the present invention is not limited thereto.
- Resin (A) preferably contains a repeating unit represented by the following general formula (4).
- R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- R 42 may be bonded to L 4 to form a ring, and R 42 in this case represents an alkylene group.
- L 4 represents a single bond or a divalent linking group, and in the case of forming a ring with R 42 , represents a trivalent linking group.
- R 44 and R 45 represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
- M 4 represents a single bond or a divalent linking group.
- Q 4 represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. At least two of Q 4 , M 4 and R 44 may be bonded to form a ring.
- R 41 , R 42 and R 43 have the same meanings as R 51 , R 52 and R 53 in the general formula (V), and preferred ranges thereof are also the same.
- L 4 has the same meaning as L 5 in the general formula (V), and the preferred range is also the same.
- R 44 and R 45 have the same meaning as R 3 in the general formula (3), and the preferred range is also the same.
- M 4 has the same meaning as M 3 in the general formula (3), and the preferred range is also the same.
- Q 4 has the same meaning as Q 3 in the general formula (3), and the preferred range is also the same.
- Examples of the ring formed by combining at least two of Q 4 , M 4 and R 44 include rings formed by combining at least two of Q 3 , M 3 and R 3 , and the preferred range is the same. It is. Specific examples of the repeating unit represented by the general formula (4) are shown below, but the present invention is not limited thereto.
- the resin (A) may contain a repeating unit represented by the following general formula (BZ) as the repeating unit (a).
- AR represents an aryl group.
- Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
- Rn and AR may be bonded to each other to form a non-aromatic ring.
- R 1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.
- repeating unit (a) represented by the general formula (BZ) are shown below, but are not limited thereto.
- the above repeating unit having an acid-decomposable group may be one type or a combination of two or more types.
- the content of the repeating unit having an acid-decomposable group in the resin (A) (when there are a plurality of types) is 5 mol% or more and 80 mol% or less with respect to all the repeating units in the resin (A). It is preferably 5 mol% or more and 75 mol% or less, more preferably 10 mol% or more and 65 mol% or less.
- Resin (A) may contain a repeating unit represented by the following general formula (V) or the following general formula (VI).
- R 6 and R 7 are each independently a hydrogen atom, a hydroxy group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, an amino group, It represents a halogen atom, an ester group (—OCOR or —COOR: R is an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group. n 3 represents an integer of 0 to 6.
- X 4 is a methylene group, an oxygen atom or a sulfur atom.
- the actinic ray-sensitive or radiation-sensitive composition preferably contains a compound that generates an acid by actinic rays or radiation (hereinafter, also referred to as “photoacid generator ⁇ PAG: Photo Acid Generator”).
- the photoacid generator 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 photoacid generator is in 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 photoacid generator When the photoacid generator is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) or in a resin different from the resin (A). In the present invention, the photoacid generator is preferably in the form of a low molecular compound.
- the photoacid generator is not particularly limited as long as it is a known one, but upon irradiation with actinic rays or radiation, preferably electron beams or extreme ultraviolet rays, an organic acid such as sulfonic acid, bis (alkylsulfonyl) imide, or Compounds that generate at least one of tris (alkylsulfonyl) methides are preferred. More preferred examples include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).
- 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 a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).
- Non-nucleophilic anions include, for example, sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphor sulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyls). Carboxylate anion, etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.
- the aliphatic moiety in the aliphatic sulfonate anion and aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. Examples include 3 to 30 cycloalkyl groups.
- the aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
- the alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms).
- an alkylthio group preferably having 1 to 15 carbon atoms
- an alkylsulfonyl group preferably having 1 to 15 carbon atoms
- an alkyliminosulfonyl group preferably having 1 to 15 carbon atoms
- an aryloxysulfonyl group preferably having carbon atoms Number 6 to 20
- alkylaryloxysulfonyl group preferably having 7 to 20 carbon atoms
- cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like.
- examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).
- aralkyl group in the aralkyl carboxylate anion preferably an aralkyl group having 7 to 12 carbon atoms such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group and the like can be mentioned.
- Examples of the sulfonylimide anion include saccharin anion.
- the alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms.
- substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like.
- a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
- the alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.
- non-nucleophilic anions examples include fluorinated phosphorus (eg, PF 6 ⁇ ), fluorinated boron (eg, BF 4 ⁇ ), fluorinated antimony (eg, SbF 6 ⁇ ), and the like. .
- non-nucleophilic anion examples include an aliphatic sulfonate anion in which at least ⁇ -position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom.
- the non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane.
- the pKa of the generated acid is preferably ⁇ 1 or less in order to improve sensitivity.
- an anion represented by the following general formula (AN1) can be mentioned as a preferred embodiment.
- Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
- R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of R 1 and R 2 , they may be the same or different.
- L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
- A represents a cyclic organic group.
- x represents an integer of 1 to 20
- y represents an integer of 0 to 10
- z represents an integer of 0 to 10.
- the alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
- the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
- Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
- Xf include fluorine atom, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 2 C 2 F 5 , CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 C 4 F 9 , CH 2 CH 2 C 4 F 9 may be mentioned, among which a fluorine atom and CF 3 are preferable. In particular, it is preferable that both Xf are fluorine atoms.
- the alkyl group of R 1 and R 2 may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferred is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent for R 1 and R 2 include CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F 11 , C 6 F 13 , and C 7 F 15.
- R 1 and R 2 are preferably a fluorine atom or CF 3 .
- x is preferably from 1 to 10, and more preferably from 1 to 5.
- y is preferably 0 to 4, more preferably 0.
- z is preferably 0 to 5, and more preferably 0 to 3.
- the divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO 2 —, an alkylene group, a cycloalkylene group, An alkenylene group or a linking group in which a plurality of these groups are linked can be exemplified, and a linking group having a total carbon number of 12 or less is preferred.
- —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.
- the cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having aromaticity but also aromaticity). And the like).
- the alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododecane group.
- a polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred.
- 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, an adamantyl group, or the like is present in the film in the post-exposure heating step. It is preferable from the viewpoint of improving diffusibility and improving MEEF (mask error enhancement factor).
- Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
- Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, those derived from a furan ring, a thiophene ring and a pyridine ring are preferred.
- examples of the cyclic organic group include lactone structures, and specific examples include lactone structures represented by the following general formulas (LC1-1) to (LC1-17).
- the cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms), cyclo Alkyl group (which may be monocyclic, polycyclic or spiro ring, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxy group, alkoxy group, ester group, amide Group, urethane group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group and the like.
- the carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.
- Examples of the organic group for R 201 , R 202, and R 203 include an aryl group, an alkyl group, and a cycloalkyl group.
- R 201 , R 202 and R 203 at least one is preferably an aryl group, more preferably all three are aryl groups.
- aryl group in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used.
- Preferred examples of the alkyl group and cycloalkyl group represented by R 201 to R 203 include a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. More preferable examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. More preferable examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
- These groups may further have a substituent.
- substituents include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.
- the photoacid generator has a volume of 130 to 3 or more by irradiation with an electron beam or extreme ultraviolet rays from the viewpoint of suppressing the diffusion of the acid generated by exposure to the non-exposed portion and improving the resolution.
- the compound generate an acid (more preferably sulfonic acid) having a size of more than 1, more preferably a compound that generates an acid having a volume of 190 3 or more (more preferably sulfonic acid).
- more preferably 270 ⁇ 3 (more preferably sulfonic acid) or a size of the acid is a compound that generates, be (more preferably sulfonic acid) acid volume 400 ⁇ 3 or more in size is a compound capable of generating an Particularly preferred.
- the volume is preferably 2000 3 or less, and more preferably 1500 3 or less.
- the volume value was determined using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example is input, and then the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method with this structure as the initial structure. By performing molecular orbital calculation using the PM3 method for these most stable conformations, the “accessible volume” of each acid can be calculated.
- the calculated value of the volume is appended to a part of the example (unit 3 3 ).
- required here is a volume value of the acid which the proton couple
- Examples of the photoacid generator include paragraphs ⁇ 0368> to ⁇ 0377> of JP2014-41328A, paragraphs ⁇ 0240> to ⁇ 0262> of JP2013-228881A (corresponding US Patent Application Publication No. 2015/004533).
- ⁇ 0339> of the specification can be incorporated, the contents of which are incorporated herein.
- the following compounds are mentioned as a preferable specific example, it is not limited to these.
- a photo-acid generator can be used individually by 1 type or in combination of 2 or more types.
- the content of the photoacid generator in the actinic ray-sensitive or radiation-sensitive composition is preferably 0.1 to 50% by mass, more preferably 5 to 50% by mass, based on the total solid content of the composition. More preferably, it is 8 to 40% by mass.
- the content of the photoacid generator is preferably high, more preferably 10 to 40% by mass, and most preferably 10 to 35% by mass.
- (C) Solvent When preparing the actinic ray-sensitive or radiation-sensitive composition by dissolving the above-described components, a solvent can be used.
- the solvent that can be used include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone having 4 to 10 carbon atoms, and ring having 4 to 10 carbon atoms.
- examples thereof may include organic solvents such as monoketone compounds, alkylene carbonates, alkyl alkoxyacetates and alkyl pyruvates.
- alkylene glycol monoalkyl ether carboxylate examples include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl Preferred examples include ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.
- alkylene glycol monoalkyl ether examples include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.
- alkyl lactate examples include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
- alkyl alkoxypropionate examples include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.
- Examples of the cyclic lactone having 4 to 10 carbon atoms include ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -methyl- ⁇ -butyrolactone, ⁇ -methyl- ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ - Preferred are caprolactone, ⁇ -octanoic lactone, and ⁇ -hydroxy- ⁇ -butyrolactone.
- Examples of the monoketone compound having 4 to 10 carbon atoms and optionally containing a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4- Methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2 -Hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4 -Heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5- Xen-2-one, 3-
- alkylene carbonate examples include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
- alkyl alkoxyacetate examples include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.
- Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.
- a solvent which can be preferably used a solvent having a boiling point of 130 ° C.
- the above solvents may be used alone or in combination of two or more.
- the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, and the like. Particularly preferred are propylene glycol monomethyl ether and ethyl lactate.
- Examples of the solvent not containing a hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, etc.
- propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone, and butyl acetate are particularly preferable, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate.
- the mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, still more preferably 20/80 to 60 /. 40.
- 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 is preferably a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.
- the solvent for example, the solvents described in JP-A-2014-219664, paragraphs 0013 to 0029 can also be used.
- the actinic ray-sensitive or radiation-sensitive composition preferably contains (E) a basic compound in order to reduce a change in performance over time from exposure to heating.
- a basic compound in order to reduce a change in performance over time from exposure to heating.
- Preferred examples of the basic compound include compounds having a structure 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 a carbon atom). 3 to 20) or an aryl group (preferably having 6 to 20 carbon atoms), wherein R 201 and R 202 may be bonded to each other to form a ring.
- 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.
- 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 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.
- Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like.
- Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. And undeca-7-ene.
- Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium.
- Examples thereof include hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide.
- the compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate.
- Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
- aniline compounds include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like.
- alkylamine derivative having a hydroxyl group and / or an ether bond examples include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine.
- aniline derivatives having a hydroxyl group and / or an ether bond examples include N, N-bis (hydroxyethyl) aniline.
- Preferred examples of the basic compound further include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.
- amine compound a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
- the amine compound is more preferably a tertiary amine compound.
- the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms).
- 6 to 12 carbon atoms may be bonded to the nitrogen atom.
- the amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed.
- the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
- an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
- ammonium salt compound a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
- the ammonium salt compound may be a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group, provided that at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom.
- the ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed.
- the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
- an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
- the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable.
- the halogen atom is particularly preferably chloride, bromide or iodide
- the sulfonate is particularly preferably an organic sulfonate having 1 to 20 carbon atoms.
- the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.
- the alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups.
- alkyl sulfonate examples include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.
- aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring.
- the benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms.
- the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl and the like.
- the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.
- An amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound.
- the phenoxy group may have a substituent.
- the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group.
- the substitution position of the substituent may be any of the 2-6 positions.
- the number of substituents may be any in the range of 1 to 5.
- oxyalkylene group between the phenoxy group and the nitrogen atom.
- the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
- an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
- the amine compound having a phenoxy group is prepared by reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether by heating, and then adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. It can be obtained by extraction with an organic solvent such as ethyl acetate or chloroform.
- a strong base such as sodium hydroxide, potassium hydroxide, tetraalkylammonium, etc.
- an organic solvent such as chloroform.
- composition according to the present invention has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation, resulting in a decrease, disappearance, or a proton acceptor property. It may further contain a compound that generates a compound that has been changed to acidity (hereinafter also referred to as compound (PA)).
- PA acidic property
- the proton acceptor functional group is a group that can interact electrostatically with a proton or a functional group having an electron.
- a functional group having a macrocyclic structure such as a cyclic polyether or a ⁇ -conjugated group. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute.
- the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.
- Examples of a preferable partial structure of the proton acceptor functional group include a crown ether, an azacrown ether, a primary to tertiary amine, a pyridine, an imidazole, and a pyrazine structure.
- the compound (PA) is decomposed by irradiation with actinic rays or radiation to generate a compound whose proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity.
- the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group.
- a proton adduct is formed from a compound having a proton acceptor functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium is reduced.
- Specific examples of the compound (PA) include the following compounds. Furthermore, as specific examples of the compound (PA), for example, those described in paragraphs 0421 to 0428 of JP2014-41328A and paragraphs 0108 to 0116 of JP2014-134686A can be used. The contents of which are incorporated herein.
- the amount of the basic compound used is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the actinic ray-sensitive or radiation-sensitive composition.
- the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment.
- the photoacid generator / basic compound (molar ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.
- the actinic ray-sensitive or radiation-sensitive composition may have a hydrophobic resin (E) separately from the resin (A).
- the hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film. However, unlike the surfactant, it is not always necessary to have a hydrophilic group in the molecule, and the polar / nonpolar substance is uniformly mixed. There is no need to contribute. Examples of the effect of adding the hydrophobic resin include control of the static / dynamic contact angle of the resist film surface with respect to water, suppression of outgas, and the like.
- the hydrophobic resin has at least 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 two or more types.
- the hydrophobic resin preferably contains a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain.
- the fluorine atom and / or silicon atom in the hydrophobic resin may be contained in the main chain of the resin or in the side chain. It may be.
- the hydrophobic resin when it contains a fluorine atom, it may be 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
- the cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
- the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
- Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in paragraph 0519 of US2012 / 0251948A1.
- the hydrophobic resin preferably includes a CH 3 partial structure in the side chain portion.
- the CH 3 partial structure contained in the side chain portion of the hydrophobic resin is intended to encompass CH 3 partial structure an ethyl group, and a propyl group having.
- methyl groups directly bonded to the main chain of the hydrophobic resin (for example, ⁇ -methyl groups of repeating units having a methacrylic acid structure) contribute to the uneven distribution of the surface of the hydrophobic resin due to the influence of the main chain. Since it is small, it is not included in the CH 3 partial structure in the present invention.
- hydrophobic resin those described in JP 2011-248019 A, JP 2010-175859 A, and JP 2012-032544 A can also be preferably used.
- a resist film can be formed on a substrate using the actinic ray-sensitive or radiation-sensitive composition, and a topcoat composition containing, for example, the hydrophobic resin is formed on the resist film.
- a topcoat composition containing, for example, the hydrophobic resin is formed on the resist film.
- the thickness of the resist film is preferably 10 to 100 nm, and the thickness of the topcoat layer is preferably 10 to 200 nm, more preferably 20 to 100 nm, and particularly preferably 40 to 80 nm.
- spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.
- an actinic ray-sensitive or radiation-sensitive composition is coated on a substrate (eg, silicon / silicon dioxide coating) used for the manufacture of precision integrated circuit elements by an appropriate coating method such as a spinner or a coater, and dried. Then, a resist film is formed. In addition, a known antireflection film can be applied in advance. Further, it is preferable to dry the resist film before forming the top coat layer. Next, the top coat composition can be applied on the obtained resist film by the same means as the resist film forming method and dried to form a top coat layer.
- the resist film having the top coat layer as an upper layer is usually irradiated with an electron beam (EB), X-rays or EUV light through a mask, preferably baked (heated) and developed. Thereby, a good pattern can be obtained.
- EB electron beam
- EUV light X-rays or EUV light
- the actinic ray-sensitive or radiation-sensitive composition may further contain a surfactant (F).
- a surfactant By containing a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used, it is possible to form a pattern with less adhesion and development defects with good sensitivity and resolution. Become.
- the surfactant it is particularly preferable to use a fluorine-based and / or silicon-based surfactant. Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in ⁇ 0276> of US Patent Application Publication No. 2008/0248425.
- F top EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Ltd.); Megafuck F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Synthetic Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); 01 (manufactured by Gemco); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or FTX-204
- the surfactant is a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). You may synthesize. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991. Further, surfactants other than fluorine-based and / or silicon-based surfactants described in ⁇ 0280> of US Patent Application Publication No. 2008/0248425 may be used.
- surfactants may be used alone or in combination of two or more.
- the actinic ray-sensitive or radiation-sensitive composition contains a surfactant
- the content thereof is preferably 0 to 2% by mass, more preferably 0.0001 to, based on the total solid content of the composition.
- the amount is 2% by mass, more preferably 0.0005 to 1% by mass.
- the actinic ray-sensitive or radiation-sensitive composition is a compound that promotes solubility in a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a developer (for example, it may further contain a phenol compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxy group.
- the actinic ray-sensitive or radiation-sensitive composition may further contain a dissolution inhibiting compound.
- the “dissolution inhibiting compound” is a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce the solubility in an organic developer.
- compositions used in the actinic ray-sensitive or radiation-sensitive composition and the pattern forming method of the present invention preferably does not contain impurities such as metals, metal salts containing halogens, acids and alkalis.
- the content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free (below 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.
- a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable.
- the filter may be a composite material obtained by combining these materials and ion exchange media. 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.
- filters having different pore diameters and / or materials may be used in combination.
- 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.
- adsorbent known adsorbents can be used.
- inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
- the processing solution of the present invention such as a developing solution and a rinsing solution
- a container for storing a processing solution for patterning a chemically amplified resist film which has a storage part.
- this container for example, the inner wall of the container in contact with the treatment liquid is subjected to a resin different from any of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or rust prevention and metal elution prevention treatment is performed.
- It is preferably a container for a processing solution for patterning of a chemically amplified resist film formed from a metal.
- An organic solvent that is to be used as a chemical amplification resist film patterning treatment solution is stored in the storage portion of the storage container, and the one discharged from the storage portion is used when the chemical amplification resist film is patterned. can do.
- the seal portion is also selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin. It is preferably formed from a resin different from one or more resins, or a metal that has been subjected to a rust prevention / metal elution prevention treatment.
- the seal part means a member capable of shutting off the accommodating part and the outside air, and can preferably include a packing, an O-ring and the like.
- the resin different from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin is preferably a perfluoro resin.
- Perfluoro resins include tetrafluoroethylene resin (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoride.
- PTFE tetrafluoroethylene resin
- PFA perfluoroalkyl vinyl ether copolymer
- FEP tetrafluoroethylene-hexafluoropropylene copolymer resin
- Ethylene-ethylene copolymer resin Ethylene-ethylene copolymer resin (ETFE), ethylene trifluoride-ethylene copolymer resin (ECTFE), vinylidene fluoride resin (PVDF), ethylene trifluoride chloride copolymer resin (PCTFE), vinyl fluoride resin ( PVF) and the like.
- Particularly preferable perfluoro resins include tetrafluoroethylene resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer resin.
- Examples of the metal in the metal subjected to the rust prevention / metal elution prevention treatment include carbon steel, alloy steel, nickel chromium steel, nickel chromium molybdenum steel, chromium steel, chromium molybdenum steel, manganese steel and the like.
- film technology as rust prevention and metal elution prevention treatment.
- metal coating variable plating
- inorganic coating variable chemical conversion treatment, glass, concrete, ceramics, etc.
- organic coating rust prevention oil, paint, rubber, plastics.
- Preferred film technology includes surface treatment with a rust inhibitor oil, a rust inhibitor, a corrosion inhibitor, a chelate compound, a peelable plastic, and a lining agent.
- pretreatment is a stage before rust prevention treatment. It is also preferable to adopt.
- a treatment for removing various corrosion factors such as chlorides and sulfates existing on the metal surface by washing and polishing can be preferably mentioned.
- the storage container include the following. ⁇ FluoroPure PFA composite drum manufactured by Entegris (Wetted inner surface; PFA resin lining) ⁇ JFE steel drums (wetted inner surface; zinc phosphate coating)
- Examples of the storage container include a storage container described in paragraphs 0013 to 0030 of JP-A-11-021393, a storage container described in paragraphs 0012 to 0024 of JP-A-10-45961, and the like.
- the treatment liquid of the present invention is for preventing static charge and preventing chemical liquid piping and various parts (filters, O-rings, tubes, etc.) from being damaged due to discharge accompanying the electrostatic charge.
- a conductive compound may be added. Although it does not restrict
- the addition amount is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less from the viewpoint of maintaining preferable development characteristics.
- SUS stainless steel
- various pipes coated with antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) should be used. it can.
- polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used for the filter and O-ring.
- the reaction solution was cooled to room temperature and dropped into 3 L of hexane to precipitate a polymer.
- the solid obtained by filtration was dissolved in 500 mL of acetone, and the acetone solution was again dropped into 3 L of hexane to precipitate the polymer.
- the solid obtained by filtration was dried under reduced pressure to obtain 160 g of 4-acetoxystyrene / 1-ethylcyclopentyl methacrylate / monomer 1 copolymer (A-1a).
- Resins (A-2) to (A-7) having the structures shown in Table 3 were synthesized in the same manner as in Synthesis Example 1 except that the monomers used were changed.
- the composition ratio (molar ratio) of the resin was calculated by 1 H-NMR (nuclear magnetic resonance) measurement.
- the weight average molecular weight (Mw: polystyrene conversion) and dispersity (Mw / Mn) of the resin were calculated by GPC (solvent: THF) measurement.
- Photoacid generator (B) As the photoacid generator, the following were used.
- ⁇ Resist composition> Each component shown in the following Table 4 was dissolved in the solvent shown in the same table. The obtained solution was filtered using a polyethylene filter having a pore size of 0.03 ⁇ m to obtain a resist composition.
- ⁇ EUV exposure evaluation> Using each resist composition described in Table 4, a resist pattern was formed by the following operation. [Application of resist composition and baking after application (PB)] Each resist composition obtained as described above was applied onto a 4-inch silicon wafer subjected to HMDS (hexamethyldisilazane) treatment, baked at 90 to 120 ° C. for 60 seconds, and a film thickness of 40 nm was obtained. A resist film was formed.
- HMDS hexamethyldisilazane
- EUV exposure The wafer on which the resist film was formed was subjected to EUV exposure with dipole illumination at an NA (lens numerical aperture) of 0.3 using an EUV exposure apparatus. Specifically, EUV exposure was performed by changing the exposure amount through a mask containing a pattern for forming a line-and-space pattern of 15 to 45 nm.
- PEB Post-exposure bake
- the amount of impurities in each developer / rinse solution shown in Table 5 was adjusted by distilling and / or filtering the raw material.
- the content of the sulfur-containing compound in each treatment solution was measured using a method defined in JIS K2541-6: 2013 “Sulfur content test method (ultraviolet fluorescence method)”. Further, the content of the compound containing phosphorus atoms in each treatment liquid was quantified by spectrophotometry as total phosphorus based on the method defined in JIS K0102: 2013.
- sensitivity The obtained resist pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.). Irradiation energy for separating and resolving at a line to space ratio of 1: 1 at a line width of 30 nm was defined as sensitivity (mJ / cm 2 ).
- An organic film forming composition DUV44 (manufactured by Brewer Science) was applied onto a 6-inch silicon wafer, and baked at 200 ° C. for 60 seconds to form an organic film having a thickness of 60 nm.
- a resist composition shown in Table 7 was applied thereon and baked at 90 to 120 ° C. for 60 seconds to form a resist film having a thickness of 40 nm.
- a line and space pattern (length: 20 nm to 17.5 nm in increments of 1.25 nm is applied to the wafer on which the resist film is formed using an electron beam irradiation apparatus (JBX6000FS / E manufactured by JEOL; acceleration voltage 50 keV). 0.12 mm in the direction and 20 drawing lines) were exposed by changing the exposure amount.
- JBX6000FS / E manufactured by JEOL acceleration voltage 50 keV
- the content of sulfur-containing compounds is reduced as described above, and the content of phosphorus-containing compounds is reduced to further reduce defect residues and further improve pattern performance such as sensitivity and limit resolution. Can be confirmed.
- the treatment liquid according to the present invention is applied to a FluoroPure PFA composite drum (wetted inner surface; PFA resin lining) manufactured by Entegris and a steel drum can (wetted inner surface; zinc phosphate coating) manufactured by JFE, as described in JP-A-2014-112176.
- a FluoroPure PFA composite drum wetted inner surface; PFA resin lining
- a steel drum can wetted inner surface; zinc phosphate coating
- JFE wetted inner surface; zinc phosphate coating
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Abstract
Description
より詳細には、本発明は、IC(Integrated Circuit、集積回路)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、さらには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などに使用される、処理液、及びパターン形成方法に関する。
このようなリソグラフィーにおいては、フォトレジスト組成物(感活性光線又は感放射線性組成物や、化学増幅型レジスト組成物とも呼ばれる)により膜を形成した後、得られた膜を現像液により現像したり、現像後の膜をリンス液で洗浄することが行われている。
例えば、特許文献1には、現像液やリンス液として、エステル系溶剤や炭化水素系溶剤を有機溶剤として含有する有機系処理液を用いることが開示されている。
このような問題に対して、発明者らが検討を重ねたところ、上記異物の原因として、特許文献1に記載されているような現像液あるいはリンス液に含まれる有機溶剤等から混入する硫黄原子を含む化合物(以下「硫黄含有化合物」ともいう。)の作用が特に大きいことを特定するに至った。すなわち、上記有機溶剤の原料由来の硫黄含有化合物が、レジストパターン中に含まれる成分と相互作用することによってリンス工程後の乾燥を経ても揮発せずにレジストパターン表面に残存し、これにより異物欠陥が生じるものと推定された。
より具体的には、以下の構成により上記目的を達成することができることを見出した。
感活性光線又は感放射線性組成物から得られるレジスト膜を、現像及び洗浄の少なくとも一方を行うために使用され、有機溶剤を含有するレジスト膜パターニング用の処理液であって、
上記処理液中、硫黄原子を含む化合物の含有量が10mmol/L以下である、処理液。
(2)
上記処理液が、現像液である、上記(1)に記載の処理液。
(3)
上記有機溶剤が、エステル系溶剤を含む、上記(2)に記載の処理液。
(4)
上記エステル系溶剤が、酢酸ブチル、酢酸アミル、酢酸イソアミル、酢酸2-メチルブチル、酢酸1-メチルブチル、酢酸ヘキシル、プロピオン酸ペンチル、プロピオン酸ヘキシル、プロピオン酸ヘプチル及びブタン酸ブチルからなる群から選ばれる少なくともいずれか1種を含む、上記(3)に記載の処理液。
(5)
上記処理液が、リンス液である、上記(1)に記載の処理液。
(6)
上記有機溶剤が、炭化水素系溶剤を含む、上記(5)に記載の処理液。
(7)
上記有機溶剤が、炭素数5以上の炭化水素系溶剤を含む、上記(6)に記載の処理液。
(8)
上記炭化水素系溶剤が、ウンデカンを含む、上記(6)又は(7)に記載の処理液。
(9)
上記処理液中、さらに、リン原子を含む化合物の含有量が10mmol/L以下である、上記(1)~(8)のいずれかに記載の処理液。
(10)
上記硫黄原子を含む化合物の沸点が190℃以上である、上記(1)~(9)のいずれかに記載の処理液。
(11)
感活性光線又は感放射線性組成物を用いてレジスト膜を形成するレジスト膜形成工程と、
上記レジスト膜を露光する露光工程と、
露光された上記レジスト膜を上記(1)、(2)、(3)、(4)、(9)又は(10)に記載の処理液によって処理する処理工程と、
を含む、パターン形成方法。
(12)
上記処理工程は、リンス液によって洗浄するリンス工程を備え、
上記リンス液が請求項(1)、(5)、(6)、(7)、(8)、(9)又は(10)に記載の処理液である、上記(11)に記載のパターン形成方法。
本発明の処理液は、感活性光線又は感放射線性組成物から得られるレジスト膜を、現像及び洗浄の少なくとも一方を行うために使用され、有機溶剤を含有するレジスト膜パターニング用の処理液である。本発明の処理液中、硫黄含有化合物の含有量が10mmol/L以下である。
本発明の処理液によれば、レジストパターンの欠陥の発生を抑制できる。この理由の詳細は未だ明らかになっていないが、以下のように推測される。
すなわち、現像液及び/又はリンス液として用いられる上記の処理液は、硫黄含有化合物の含有量が少ないので、処理液に含まれる硫黄含有化合物と、露光後の膜(レジスト膜)に含まれる成分、特には、ポリマー成分中の極性基、との反応を抑制できる。その結果、硫黄含有化合物とポリマー成分中の極性基等との反応によってレジストパターンの表面に生じる異物を抑制できるので、レジストパターンの欠陥の発生を抑制できると推測される。
また、特に、より後に行われる工程で用いられる処理液において硫黄含有化合物量がより低減されていることが好ましく、すなわち、リンス液に本発明の処理液を用いることが好ましい。
このように、硫黄含有化合物の含有量を10mmol/L以下とすることで、例えば処理液を収容容器(例えば、特開2014-112176号公報に記載の容器)の栓を閉じた状態にして、室温(23℃)で6ヶ月間保存した後に使用しても、レジストパターンにおける欠陥の発生を抑制できる。
ここで、「実質的に含有しない」とは、硫黄含有化合物の含有量(濃度)を測定可能な方法(例えば、後述する測定方法)で測定した場合において、検出されないこと(検出限界値未満であること)をいう。
なお、硫黄含有化合物の含有量(濃度)の下限としては、上述したように、実質的に含有しないことが最も好ましい。ただし、後述するように、硫黄含有化合物の含有量を低減させるために蒸留などの処理を過度に行うとコストがかさむ。工業的に使用する際のコストなどを考慮すると、硫黄含有化合物の含有量としては、0.01mmol/L以上であってもよい。
チオール類は、具体的には、例えば、メタンチオール、エタンチオール(エチルメルカプタン)、3-メチル-2-ブテン-1-チオール、2-メチル-3-フランチオール、フルフリルチオール(フルフリルメルカプタン)、3-メルカプト-3-メチルブチルフォーメイト、フェニルメルカプタン、メチルフルフリルメルカプタン、3-メルカプトブタン酸エチル、3-メルカプト-3-メチルブタノール、4-メルカプト-4-メチル-2-ペンタノン、などが挙げられる。
スルフィド類としては、ジメチルスルフィド、ジメチルトリサルファイド、ジイソプロピルトリスルフィド、ビス(2-メチル-3-フリル)ジスルフィド、などが挙げられる。
チオフェン類としては、例えば、様々に置換された、アルキルチオフェン類、ベンゾチオフェン類、ジベンゾチオフェン類、フェナントロチオフェン類、ベンゾナフトチオフェン類、チオフェンスルフィド類などが挙げられる。
これらの中でも、チオフェン類、特にはベンゾチオフェン類(例えば、ベンゾチオフェンや3-メチルベンゾチオフェン等)の含有量を10mmol/L以下とすることで、レジストパターンの欠陥の発生をより抑制できる。
したがって、本発明の処理液は、リン原子を含む化合物の含有量が10mmol/L以下であることが好ましく、5mmol/L以下であることがより好ましく、2.5mmol/L以下であることがさらに好ましく、1.0mmol/L以下であることが特に好ましく、実質的にリン原子を含む化合物を含有しないことがより好ましい。
なお、リン含有化合物の含有量(濃度)の下限としては、上述したように、実質的に含有しないことが最も好ましい。ただし、後述するように、リン含有化合物の含有量を低減させるために蒸留などの処理を過度に行うとコストがかさむ。工業的に使用する際のコストなどを考慮すると、リン含有化合物の含有量としては、0.01mmol/L以上であってもよい。
処理液に含まれる有機溶剤、及び含まれ得る酸化防止剤及び界面活性剤については、後述する現像液及びリンス液に関する説明で詳述する。
以下、現像液、リンス液の順に、これらに含まれる成分及び含まれ得る成分について、詳細に説明する。
本発明の処理液の一種である現像液は、後述する現像工程で用いられ、有機溶剤を含有することから有機系現像液ということもできる。
有機溶剤の蒸気圧(混合溶媒である場合は全体としての蒸気圧)は、20℃に於いて、5kPa以下が好ましく、3kPa以下が更に好ましく、2kPa以下が特に好ましい。
有機溶剤の蒸気圧を5kPa以下にすることにより、現像液の基板上あるいは現像カップ内での蒸発が抑制され、ウエハ面内の温度均一性が向上し、結果としてウエハ面内の寸法均一性が良化する。
現像液に用いられる有機溶剤としては、種々の有機溶剤が広く使用されるが、たとえば、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、炭化水素系溶剤等の溶剤を用いることができる。
特に、ケトン系溶剤、エステル系溶剤、アルコール系溶剤及びエーテル系溶剤から選択される少なくとも1種類の溶剤を含有する現像液であることが好ましい。
また、炭化水素系溶剤としては、不飽和炭化水素系溶剤も用いることができ、例えば、オクテン、ノネン、デセン、ウンデセン、ドデセン、ヘキサデセン等の不飽和炭化水素系溶剤が挙げられる。不飽和炭化水素溶剤が有する二重結合、三重結合の数は特に限定されず、また、炭化水素鎖のどの位置に有してもよい。また、不飽和炭化水素溶剤が二重結合を有する場合には、cis体及びtrans体が混在していてもよい。
なお、炭化水素系溶剤である脂肪族炭化水素系溶剤においては、同じ炭素数で異なる構造の化合物の混合物であってもよい。例えば、脂肪族炭化水素系溶媒としてデカンを使用した場合、同じ炭素数で異なる構造の化合物である2-メチルノナン、2,2-ジメチルオクタン、4-エチルオクタン、イソオクタンなどが脂肪族炭化水素系溶媒に含まれていてもよい。
また、上記同じ炭素数で異なる構造の化合物は、1種のみが含まれていてもよいし、上記のように複数種含まれていてもよい。
上記エステル系溶剤のヘテロ原子は、炭素原子及び水素原子以外の原子であって、例えば、酸素原子、窒素原子、硫黄原子等が挙げられる。ヘテロ原子数は、2以下が好ましい。
炭素原子数が7以上かつヘテロ原子数が2以下のエステル系溶剤の好ましい例としては、酢酸アミル、酢酸イソアミル、酢酸2-メチルブチル、酢酸1-メチルブチル、酢酸ヘキシル、プロピオン酸ペンチル、プロピオン酸ヘキシル、プロピオン酸ヘプチル、ブタン酸ブチルなどが挙げられ、酢酸イソアミルを用いることが特に好ましい。
エステル系溶剤と炭化水素系溶剤とを組み合わせて用いる場合には、エステル系溶剤として酢酸イソアミルを用いることが好ましい。また、炭化水素系溶剤としては、レジスト膜の溶解性を調製するという観点から、飽和炭化水素溶剤(例えば、オクタン、ノナン、デカン、ドデカン、ウンデカン、ヘキサデカンなど)を用いることが好ましい。
ケトン系溶剤と炭化水素系溶剤とを組み合わせて用いる場合には、ケトン系溶剤として2-ヘプタノンを用いることが好ましい。また、炭化水素系溶剤としては、レジスト膜の溶解性を調製するという観点から、飽和炭化水素溶剤(例えば、オクタン、ノナン、デカン、ドデカン、ウンデカン、ヘキサデカンなど)を用いることが好ましい。
また、エステル系溶剤と炭化水素系溶剤とを組み合わせて用いる場合、ケトン系溶剤と炭化水素系溶剤とを組み合わせて用いる場合には、炭化水素系溶剤として不飽和炭化水素系溶剤も用いることができ、例えば、オクテン、ノネン、デセン、ウンデセン、ドデセン、ヘキサデセン等の不飽和炭化水素系溶剤が挙げられる。不飽和炭化水素溶剤が有する二重結合、三重結合の数は特に限定されず、また、炭化水素鎖のどの位置に有してもよい。
また、不飽和炭化水素溶剤が二重結合を有する場合には、cis体及びtrans体が混在していてもよい。
上記の混合溶剤を用いる場合において、炭化水素系溶剤の含有量は、レジスト膜の溶剤溶解性に依存するため、特に限定されず、適宜調製して必要量を決定すればよい。
現像液における有機溶剤(複数混合の場合は合計)の濃度は、好ましくは50質量%以上、より好ましくは50~100質量%、さらに好ましくは85~90質量%以上、特に好ましくは95~100質量%である。最も好ましくは、実質的に有機溶剤のみからなる場合である。なお、実質的に有機溶剤のみからなる場合とは、微量の界面活性剤、酸化防止剤、安定剤、消泡剤などを含有する場合を含むものとする。
エステル系溶剤としては、後述する一般式(S1)で表される溶剤又は後述する一般式(S2)で表される溶剤を用いることがより好ましく、一般式(S1)で表される溶剤を用いることが更により好ましく、酢酸アルキルを用いることが特に好ましく、酢酸ブチル、酢酸アミル(酢酸ペンチル)、酢酸イソアミル(酢酸イソペンチル)を用いることが最も好ましい。
R及びR’についてのアルキル基、アルコキシル基、アルコキシカルボニル基の炭素数は、1~15の範囲であることが好ましく、シクロアルキル基の炭素数は、3~15であることが好ましい。
R及びR’としては水素原子又はアルキル基が好ましく、R及びR’についてのアルキル基、シクロアルキル基、アルコキシル基、アルコキシカルボニル基、及びRとR’とが互いに結合して形成する環は、水酸基、カルボニル基を含む基(例えば、アシル基、アルデヒド基、アルコキシカルボニル等)、シアノ基などで置換されていてもよい。
一般式(S1)で表される溶剤としては、酢酸アルキルであることが好ましく、酢酸ブチル、酢酸アミル(酢酸ペンチル)、酢酸イソアミル(酢酸イソペンチル)であることがより好ましく、酢酸イソアミルであることがさらに好ましい。
R’’及びR’’’’は、各々独立に、水素原子、アルキル基、シクロアルキル基、アルコキシル基、アルコキシカルボニル基、カルボキシル基、ヒドロキシル基、シアノ基又はハロゲン原子を表す。R’’及びR’’’’は、互いに結合して環を形成してもよい。
R’’及びR’’’’は、水素原子又はアルキル基であることが好ましい。R’’及びR’’’’についてのアルキル基、アルコキシル基、アルコキシカルボニル基の炭素数は、1~15の範囲であることが好ましく、シクロアルキル基の炭素数は、3~15であることが好ましい。
R’’’は、アルキレン基又はシクロアルキレン基を表す。R’’’は、アルキレン基であることが好ましい。R’’’についてのアルキレン基の炭素数は、1~10の範囲であることが好ましい。R’’’についてのシクロアルキレン基の炭素数は、3~10の範囲であることが好ましい。
R’’及びR’’’’についてのアルキル基、シクロアルキル基、アルコキシル基、アルコキシカルボニル基、R’’’についてのアルキレン基、シクロアルキレン基、及びR’’とR’’’’とが互いに結合して形成する環は、水酸基、カルボニル基を含む基(例えば、アシル基、アルデヒド基、アルコキシカルボニル等)、シアノ基などで置換されていてもよい。
これらの中でも、R’’及びR’’’’が無置換のアルキル基であり、R’’’が無置換のアルキレン基であることが好ましく、R’’及びR’’’’がメチル基及びエチル基のいずれかであることがより好ましく、R’’及びR’’’’がメチル基であることが更により好ましい。
用いることができるエーテル系溶剤としては、前述のエーテル系溶剤が挙げられ、このなかでも芳香環を一つ以上含むエーテル系溶剤が好まく、下記一般式(S3)で表される溶剤がより好ましく、最も好ましくはアニソールである。
RSは、アルキル基を表す。アルキル基としては炭素数1~4が好ましく、メチル基又はエチル基がより好ましく、メチル基であることが最も好ましい。
現像液は、界面活性剤を含有することが好ましい。これにより、レジスト膜に対する濡れ性が向上して、現像がより効果的に進行する。
界面活性剤としては、後述する感活性光線又は感放射線性組成物に用いられる界面活性剤と同様のものを用いることができる。
界面活性剤の含有量は、現像液の全質量に対して、通常0.001~5質量%、好ましくは0.005~2質量%、更に好ましくは0.01~0.5質量%である。
現像液は、酸化防止剤を含有することが好ましい。これにより、経時的な酸化剤の発生を抑制でき、酸化剤の含有量をより低下できる。
アミン系酸化防止剤としては、例えば、1-ナフチルアミン、フェニル-1-ナフチルアミン、p-オクチルフェニル-1-ナフチルアミン、p-ノニルフェニル-1-ナフチルアミン、p-ドデシルフェニル-1-ナフチルアミン、フェニル-2-ナフチルアミン等のナフチルアミン系酸化防止剤;N,N'-ジイソプロピル-p-フェニレンジアミン、N,N'-ジイソブチル-p-フェニレンジアミン、N,N'-ジフェニル-p-フェニレンジアミン、N,N'-ジ-β-ナフチル-p-フェニレンジアミン、N-フェニル-N'-イソプロピル-p-フェニレンジアミン、N-シクロヘキシル-N'-フェニル-p-フェニレンジアミン、N-1,3-ジメチルブチル-N'-フェニル-p-フェニレンジアミン、ジオクチル-p-フェニレンジアミン、フェニルヘキシル-p-フェニレンジアミン、フェニルオクチル-p-フェニレンジアミン等のフェニレンジアミン系酸化防止剤;ジピリジルアミン、ジフェニルアミン、p,p'-ジ-n-ブチルジフェニルアミン、p,p'-ジ-t-ブチルジフェニルアミン、p,p'-ジ-t-ペンチルジフェニルアミン、p,p'-ジオクチルジフェニルアミン、p,p'-ジノニルジフェニルアミン、p,p'-ジデシルジフェニルアミン、p,p'-ジドデシルジフェニルアミン、p,p'-ジスチリルジフェニルアミン、p,p'-ジメトキシジフェニルアミン、4,4'-ビス(4-α,α-ジメチルベンゾイル)ジフェニルアミン、p-イソプロポキシジフェニルアミン、ジピリジルアミン等のジフェニルアミン系酸化防止剤;フェノチアジン、N-メチルフェノチアジン、N-エチルフェノチアジン、3,7-ジオクチルフェノチアジン、フェノチアジンカルボン酸エステル、フェノセレナジン等のフェノチアジン系酸化防止剤が挙げられる。
フェノール系酸化防止剤としては、例えば、例えば、2,6-ジ-ターシャリブチルフェノール(以下、ターシャリブチルをt-ブチルと略記する。)、2,6-ジ-t-ブチル-p-クレゾール、2,6-ジ-t-ブチル-4-メチルフェノール、2,6-ジ-t-ブチル-4-エチルフェノール、2,4-ジメチル-6-t-ブチルフェノール、4,4’-メチレンビス(2,6-ジ-t-ブチルフェノール)、4,4’-ビス(2,6-ジ-t-ブチルフェノール)、4,4’-ビス(2-メチル-6-t-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、2,2’-メチレンビス(4-エチル-6-t-ブチルフェノール)、4,4’-ブチリデンビス(3-メチル-6-t-ブチルフェノール)、4,4’-イソプロピリデンビス(2,6-ジ-t-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-シクロヘキシルフェノール)、2,2’-メチレンビス(4-メチル-6-ノニルフェノール)、2,2’-イソブチリデンビス(4,6-ジメチルフェノール)、2,6-ビス(2’-ヒドロキシ-3’-t-ブチル-5’-メチルベンジル)-4-メチルフェノール、3-t-ブチル-4-ヒドロキシアニソール、2-t-ブチル-4-ヒドロキシアニソール、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸オクチル、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸ステアリル、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸オレイル、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸ドデシル、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸デシル、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸オクチル、テトラキス{3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオニルオキシメチル}メタン、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸グリセリンモノエステル、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸とグリセリンモノオレイルエーテルとのエステル、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸ブチレングリコールジエステル、2,6-ジ-t-ブチル-α-ジメチルアミノ-p-クレゾール、2,6-ジ-t-ブチル-4-(N,N’-ジメチルアミノメチルフェノール)、トリス{(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオニル―オキシエチル}イソシアヌレート、トリス(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)イソシアヌレート、1,3,5-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)イソシアヌレート、1,3,5-トリス(4-t-ブチル-3-ヒドロキシ-2,6―ジメチルベンジル)イソシアヌレート、N,N’-ヘキサメチレンビス(3,5-ジ-t-ブチル-4-ヒドロキシ-ヒドロシナミド)、3,9-ビス〔1,1-ジメチル-2-{β-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ}エチル〕-2,4,8,10-テトラオキサスピロ[5,5]ウンデカン、1,1,3-トリス(2-メチル-4-ヒドロキシ-5-t-ブチルフェニル)ブタン、1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)ベンゼン、ビス{3,3’-ビス-(4’-ヒドロキシ-3’-t-ブチルフェニル)ブチリックアシッド}グリコールエステル等が挙げられる。
本発明の現像液は、塩基性化合物を含有することが好ましい。塩基性化合物の具体例としては、後に述べる感活性光線性又は感放射線性組成物が含み得る塩基性化合物(E)として例示する化合物が挙げられる。
本発明の現像液に含まれ得る塩基性化合物の中でも、以下の含窒素化合物を好ましく用いることができる。
SP値(Fedors法)=[(各置換基の凝集エネルギーの和)/(各置換基の体積の和)]0.5
なお、本発明において、上記の含窒素化合物は、1種のみを使用してもよいし、化学構造が異なる2種以上を併用してもよい。
本発明の処理液の一種であるリンス液は、後述するリンス工程で用いられ、有機溶剤を含有することから有機系リンス液ということもできる。本発明の処理液を用いたレジスト膜の「洗浄」(すなわち、レジスト膜の「リンス」)には、このリンス液が用いられる。
本発明のリンス液に含まれる有機溶剤としては、種々の有機溶剤が用いられるが、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種の有機溶剤を用いることが好ましい。
これらの有機溶剤の具体例は、上記現像液で説明した有機溶剤と同様である。
なお、上記脂肪族炭化水素系溶剤の炭素原子数の上限値は特に限定されないが、例えば、16以下が挙げられ、14以下が好ましく、12以下がより好ましい。
上記脂肪側炭化水素系溶剤の中でも、特に好ましくは、デカン、ウンデカン、ドデカンであり、最も好ましくはウンデカンである。
尚、リンス液に含まれる炭化水素系溶剤として不飽和炭化水素系溶剤も用いることができ、例えば、オクテン、ノネン、デセン、ウンデセン、ドデセン、ヘキサデセン等の不飽和炭化水素系溶剤が挙げられる。不飽和炭化水素溶剤が有する二重結合、三重結合の数は特に限定されず、また、炭化水素鎖のどの位置に有してもよい。また、不飽和炭化水素溶剤が二重結合を有する場合には、cis体及びtrans体が混在していてもよい。
このようにリンス液に含まれる有機溶剤として炭化水素系溶剤(特に脂肪族炭化水素系溶剤)を用いることで、現像後にわずかにレジスト膜に染み込んでいた現像液が洗い流されて、膨潤がより抑制され、パターン倒れが抑制されるという効果が一層発揮される。
エステル系溶剤と炭化水素系溶剤とを組み合わせて用いる場合には、エステル系溶剤として酢酸ブチル、酢酸イソアミルを用いることが好ましい。また、炭化水素系溶剤としては、上記効果が一層発揮されるという点から、飽和炭化水素溶剤(例えば、デカン、ドデカン、ウンデカン、ヘキサデカンなど)を用いることが好ましい。
ケトン系溶剤と炭化水素系溶剤とを組み合わせて用いる場合には、ケトン系溶剤として2-ヘプタノンを用いることが好ましい。また、炭化水素系溶剤としては、上記効果が一層発揮されるという点から、飽和炭化水素溶剤(例えば、デカン、ドデカン、ウンデカン、ヘキサデカンなど)を用いることが好ましい。
また、エステル系溶剤と炭化水素系溶剤とを組み合わせて用いる場合、ケトン系溶剤と炭化水素系溶剤とを組み合わせて用いる場合には、炭化水素系溶剤として不飽和炭化水素系溶剤も用いることができ、例えば、オクテン、ノネン、デセン、ウンデセン、ドデセン、ヘキサデセン等の不飽和炭化水素系溶剤が挙げられる。不飽和炭化水素溶剤が有する二重結合、三重結合の数は特に限定されず、また、炭化水素鎖のどの位置に有してもよい。
また、不飽和炭化水素溶剤が二重結合を有する場合には、cis体及びtrans体が混在していてもよい。
リンス液が、エステル系溶剤及びケトン系溶剤からなる群より選択される少なくとも1種を含有する場合、酢酸ブチル、酢酸イソペンチル(酢酸イソアミル)、酢酸n-ペンチル、3-エトキシプロピオン酸エチル(EEP、エチル-3-エトキシプロピオネート)、及び2-ヘプタノンからなる群より選択される少なくとも1種の溶剤を主成分として含有することが好ましく、酢酸ブチル及び2-ヘプタノンからなる群より選択される少なくとも1種の溶剤を主成分として含有することが特に好ましい。
また、リンス液が、エステル系溶剤及びケトン系溶剤からなる群より選択される少なくとも1種を含有する場合、エステル系溶剤、グリコールエーテル系溶剤、ケトン系溶剤、アルコール系溶剤からなる群より選択される溶剤を副成分として含有することが好ましく、中でも、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)、プロピレングリコールモノメチルエーテル(PGME)、酢酸エチル、乳酸エチル、3-メトキシプロピオン酸メチル、シクロヘキサノン、メチルエチルケトン、γ-ブチロラクトン、プロパノール、3-メトキシ-1-ブタノール、N-メチルピロリドン、プロピレンカーボネートからなる群より選択される溶剤が好ましい。
この中でも、有機溶剤としてエステル系溶剤を用いる場合には、上記効果が一層発揮されるという点から、2種以上のエステル系溶剤を用いることが好ましい。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、これとは化学構造が異なるエステル系溶剤(好ましくは、プロピレングリコールモノメチルエーテルアセテート(PGMEA))を副成分として用いることが挙げられる。
また、有機溶剤としてエステル系溶剤を用いる場合には、上記効果が一層発揮されるという点から、エステル系溶剤(1種又は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。
有機溶剤としてケトン系溶剤を用いる場合には、上記効果が一層発揮されるという点から、ケトン系溶剤(1種又は2種以上)に加えて、エステル系溶剤及び/又は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、ケトン系溶剤(好ましくは2-ヘプタノン)を主成分として、エステル系溶剤(好ましくは、プロピレングリコールモノメチルエーテルアセテート(PGMEA))及び/又は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。
ここで、上記の「主成分」とは、有機溶剤の全質量に対する含有量が、50~100質量%であることをいい、好ましくは70~100質量%、より好ましくは80~100質量%、さらに好ましくは90~100質量%、特に好ましくは95~100質量%であることをいう。
また、副成分を含有する場合には、副成分の含有量は、主成分の全質量(100質量%)に対して、0.1~20質量%であることが好ましく、0.5~10質量%であることがより好ましく、1~5質量%であることがさらに好ましい。
界面活性剤としては、後述する感活性光線又は感放射線性組成物に用いられる界面活性剤と同様のものを用いることができる。
界面活性剤の含有量は、リンス液の全質量に対して、通常0.001~5質量%、好ましくは0.005~2質量%、更に好ましくは0.01~0.5質量%である。
非化学増幅系のレジストとしては、例えば、下記のものが挙げられる。
(1)g線、h線、i線、KrF、ArF、EBあるいはEUV等の照射によって主鎖が切断し、分子量が低下することにより溶解性が変化するレジスト材料(例えば特開2013-210411号公報の段落0025~0029、0056や米国特許公報2015/0008211の段落0032~0036、0063に記載のα-クロロアクリル酸エステル系化合物とα-メチルスチレン系化合物との共重合体を主成分とするレジスト材料等)
(2)g線、h線、i線、KrF、ArF、EBあるいはEUV等によって生じたシラノール縮合反応を伴うハイドロゲンシルセスオキサン(HSQ)、塩素置換したカリックスアレーン等のレジスト材料
(3)g線、h線、i線、KrF、ArF、EBあるいはEUV等の光に対して吸収を有する金属錯体(マグネシウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、銀、カドミウム、インジウム、錫、アンチモン、セシウム、ジルコニウム、ハフニウム等の錯体であり、チタン、ジルコニウム、ハフニウムがパターン形成性の観点から好ましい)を含み、配位子脱離や光酸発生剤と併用して配位子交換過程を伴うレジスト(特開2015-075500号公報の段落0017~0033、0037~0047、特開2012-185485号公報の段落0017~0032、0043~0044、米国特許公報2012/0208125の段落0042~0051、0066等に記載のレジスト材料)等。
シリコン系のレジストとしては、例えば、特開2008-83384号公報に記載の段落0010~0062、段落0129~0165に記載のレジスト材料が挙げられる。
本発明のパターン形成方法は、感活性光線又は感放射線性組成物(以下「レジスト組成物」ともいう。)を用いてレジスト膜を形成するレジスト膜形成工程と、上記レジスト膜を露光する露光工程と、露光された上記レジスト膜を上述した処理液(硫黄含有化合物の含有量が10mmol/L以下である処理液)によって処理する処理工程と、を含む。
本発明のパターン形成方法によれば、上述した処理液を用いるので、レジストパターンの欠陥の発生を抑制できる。
レジスト膜形成工程は、感活性光線性又は感放射線性組成物を用いてレジスト膜を形成する工程であり、例えば次の方法により行うことができる。
感活性光線性又は感放射線性組成物を用いて基板上にレジスト膜(感活性光線性又は感放射線性組成物膜)を形成するためには、後述する各成分を溶剤に溶解して感活性光線性又は感放射線性組成物を調製し、必要に応じてフィルター濾過した後、基板上に塗布する。フィルターとしては、ポアサイズ0.1ミクロン以下、より好ましくは0.05ミクロン以下、更に好ましくは0.03ミクロン以下のポリテトラフロロエチレン製、ポリエチレン製、ナイロン製のものが好ましい。
加熱温度は80~150℃で行うことが好ましく、80~140℃で行うことがより好ましく、80~130℃で行うことが更に好ましい。加熱時間は30~1000秒が好ましく、60~800秒がより好ましく、60~600秒が更に好ましい。
例えば30nm以下のサイズの1:1ラインアンドスペースパターンを解像させるためには、形成されるレジスト膜の膜厚が50nm以下であることが好ましい。膜厚が50nm以下であれば、後述する現像工程を適用した際に、パターン倒れがより起こりにくくなり、より優れた解像性能が得られる。
膜厚の範囲としてより好ましくは、15nmから45nmの範囲である。膜厚が15nm以上であれば、十分なエッチング耐性が得られる。膜厚の範囲として更に好ましくは、15nmから40nmである。膜厚がこの範囲にあると、エッチング耐性とより優れた解像性能とを同時に満足させることができる。
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。
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、例えば、特開2013-61648号公報に記載されたような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。トップコートが含み得る塩基性化合物の具体的な例は、塩基性化合物(E)として後述する。
また、トップコートは、エーテル結合、チオエーテル結合、ヒドロキシル基、チオール基、カルボニル結合及びエステル結合からなる群より選択される基又は結合を少なくとも一つ含む化合物を含むことが好ましい。
露光工程は、上記レジスト膜を露光する工程であり、例えば次の方法により行うことができる。
上記のようにして形成したレジスト膜に、所定のマスクを通して活性光線又は放射線を照射する。なお、電子ビームの照射では、マスクを介さない描画(直描)が一般的である。
活性光線又は放射線としては特に限定されないが、例えばKrFエキシマレーザー、ArFエキシマレーザー、EUV光(Extreme Ultra Violet)、電子線(EB、Electron Beam)等である。露光は液浸露光であってもよい。
本発明のパターン形成方法においては、露光後、現像を行う前にベーク(加熱)を行うことが好ましい。ベークにより露光部の反応が促進され、感度やパターン形状がより良好となる。
加熱温度は80~150℃が好ましく、80~140℃がより好ましく、80~130℃が更に好ましい。
加熱時間は30~1000秒が好ましく、60~800秒がより好ましく、60~600秒が更に好ましい。
加熱は通常の露光・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。
現像工程は、露光された上記レジスト膜を現像液によって現像する工程である。
また、現像を行う工程の後に、他の溶媒に置換しながら、現像を停止する工程を実施してもよい。
現像時間は未露光部の樹脂が十分に溶解する時間であれば特に制限はなく、通常は10~300秒であり、好ましくは20~120秒である。
現像液の温度は0~50℃が好ましく、15~35℃がより好ましい。
リンス工程は、上記現像工程の後にリンス液によって洗浄(リンス)する工程である。
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(回転吐出法)、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、この中でも回転吐出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。
リンス時間には特に制限はないが、通常は10秒~300秒であり。好ましくは10秒~180秒であり、最も好ましくは20秒~120秒である。
リンス液の温度は0~50℃が好ましく、15~35℃が更に好ましい。
さらに、現像処理又はリンス処理又は超臨界流体による処理の後、パターン中に残存する溶剤を除去するために加熱処理を行うことができる。加熱温度は、良好なレジストパターンが得られる限り特に限定されるものではなく、通常40~160℃である。加熱温度は50~150℃が好ましく、50~110℃が最も好ましい。加熱時間に関しては良好なレジストパターンが得られる限り特に限定されないが、通常15~300秒であり、好ましくは、15~180秒である。
上記問題を解決するためには、再度、レジストが溶解する溶媒を配管に通す方法がある。配管に通す方法としては、リンス液での洗浄後に基板の背面や側面などをレジストが溶解する溶媒で洗浄して流す方法や、レジストに接触させずにレジストが溶解する溶剤を配管を通るように流す方法が挙げられる。
配管に通す溶剤としては、レジストを溶解し得るものであれば特に限定されず、例えば上述した有機溶媒が挙げられ、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)、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルプロピオネート、プロピレングリコールモノエチルエーテルプロピオネート、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテル(PGME)、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、2-ヘプタノン、乳酸エチル、1-プロパノール、アセトン、等を用いることができる。中でも好ましくは、PGMEA,PGME,シクロヘキサノンを用いることができる。
次に、本発明の処理液を組み合わせて用いることが好ましい感活性光線性又は感放射線性組成物について詳細に説明する。
<樹脂(A)>
本発明の処理液と組み合わせて用いることが好ましい感活性光線性又は感放射線性組成物としては、樹脂(A)を含有することが好ましい。樹脂(A)は、少なくとも(i)酸の作用により分解してカルボキシル基を生じる基を有する繰り返し単位(さらに、フェノール性水酸基を有する繰り返し単位を有してもよい)、又は、少なくとも(ii)フェノール系水酸基を有する繰り返し単位を有する。
なお、酸の作用により分解してカルボキシル基を有する繰り返し単位を有すると、酸の作用によりアルカリ現像液に対する溶解度が増大し、有機溶剤に対する溶解度が減少する。
R41、R42及びR43は、各々独立に、水素原子、アルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。但し、R42はAr4と結合して環を形成していてもよく、その場合のR42は単結合又はアルキレン基を表す。
X4は、単結合、-COO-、又は-CONR64-を表し、R64は、水素原子又はアルキル基を表す。
L4は、単結合又はアルキレン基を表す。
Ar4は、(n+1)価の芳香環基を表し、R42と結合して環を形成する場合には(n+2)価の芳香環基を表す。
nは、1~5の整数を表す。
一般式(I)におけるR41、R42、R43のハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられ、フッ素原子が特に好ましい。
一般式(I)におけるR41、R42、R43のアルコキシカルボニル基に含まれるアルキル基としては、上記R41、R42、R43におけるアルキル基と同様のものが好ましい。
(n+1)価の芳香環基は、更に置換基を有していてもよい。
X4により表わされる-CONR64-(R64は、水素原子、アルキル基を表す)におけるR64のアルキル基としては、好ましくは置換基を有していてもよいメチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、sec-ブチル基、ヘキシル基、2-エチルヘキシル基、オクチル基、ドデシル基など炭素数20以下のアルキル基が挙げられ、より好ましくは炭素数8以下のアルキル基が挙げられる。
X4としては、単結合、-COO-、-CONH-が好ましく、単結合、-COO-がより好ましい。
Ar4としては、置換基を有していてもよい炭素数6~18の芳香環基がより好ましく、ベンゼン環基、ナフタレン環基、ビフェニレン環基が特に好ましい。
一般式(I)で表される繰り返し単位は、ヒドロキシスチレン構造を備えていることが好ましい。即ち、Ar4は、ベンゼン環基であることが好ましい。
式中、R36~R39は、各々独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。R36とR37とは、互いに結合して環を形成してもよい。
R01及びR02は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。
Xa1は、水素原子、置換基を有していてもよいアルキル基を表す。
Tは、単結合又は2価の連結基を表す。
Rx1~Rx3は、各々独立に、アルキル基(直鎖若しくは分岐)又はシクロアルキル基(単環若しくは多環)を表す。ただし、Rx1~Rx3の全てがアルキル基(直鎖若しくは分岐)である場合、Rx1~Rx3のうち少なくとも2つはメチル基であることが好ましい。
Rx1~Rx3の2つが結合して、シクロアルキル基(単環若しくは多環)を形成してもよい。
Tの2価の連結基としては、アルキレン基、-COO-Rt-基、-O-Rt-基等が挙げられる。式中、Rtは、アルキレン基又はシクロアルキレン基を表す。
Tは、単結合又は-COO-Rt-基が好ましい。Rtは、炭素数1~5のアルキレン基が好ましく、-CH2-基、-(CH2)2-基、-(CH2)3-基がより好ましい。
Rx1~Rx3のシクロアルキル基としては、シクロペンチル基、シクロヘキシル基などの単環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多環のシクロアルキル基が好ましい。
Rx1~Rx3の2つが結合して形成されるシクロアルキル基としては、シクロペンチル基、シクロヘキシル基などの単環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多環のシクロアルキル基が好ましい。炭素数5~6の単環のシクロアルキル基が特に好ましい。
Rx1~Rx3の2つが結合して形成されるシクロアルキル基は、例えば、環を構成するメチレン基の1つが、酸素原子等のヘテロ原子、又は、カルボニル基等のヘテロ原子を有する基で置き換わっていてもよい。
一般式(AI)で表される繰り返し単位は、例えば、Rx1がメチル基又はエチル基であり、Rx2とRx3とが結合して上述のシクロアルキル基を形成している態様が好ましい。
具体例中、Rx、Xa1は、水素原子、CH3、CF3、又はCH2OHを表す。Rxa、Rxbは各々炭素数1~4のアルキル基を表す。Zは、極性基を含む置換基を表し、複数存在する場合は各々独立である。pは0又は正の整数を表す。Zにより表される極性基を含む置換基としては、例えば、水酸基、シアノ基、アミノ基、アルキルアミド基又はスルホンアミド基を有する、直鎖又は分岐のアルキル基、シクロアルキル基が挙げられ、好ましくは、水酸基を有するアルキル基である。分岐状アルキル基としてはイソプロピル基が特に好ましい。
ラクトン基としては、ラクトン構造を含有していればいずれの基でも用いることができるが、好ましくは5~7員環ラクトン構造を含有する基であり、5~7員環ラクトン構造にビシクロ構造、スピロ構造を形成する形で他の環構造が縮環しているものが好ましい。
下記一般式(LC1-1)~(LC1-16)のいずれかで表されるラクトン構造を有する基を有する繰り返し単位を有することがより好ましい。また、ラクトン構造を有する基が主鎖に直接結合していてもよい。好ましいラクトン構造としては一般式(LC1-1)、(LC1-4)、(LC1-5)、(LC1-6)、(LC1-13)、(LC1-14)で表される基である。
Rb0のアルキル基が有していてもよい好ましい置換基としては、水酸基、ハロゲン原子が挙げられる。
Rb0のハロゲン原子としては、フッ素原子、塩素原子、臭素原子、沃素原子を挙げることができる。Rb0は、水素原子又はメチル基が好ましい。
Abは、単結合、アルキレン基、単環又は多環の脂環炭化水素構造を有する2価の連結基、エーテル基、エステル基、カルボニル基、カルボキシル基、又はこれらを組み合わせた2価の基を表す。好ましくは、単結合、-Ab1-CO2-で表される連結基である。Ab1は、直鎖、分岐アルキレン基、単環又は多環のシクロアルキレン基であり、好ましくは、メチレン基、エチレン基、シクロヘキシレン基、アダマンチレン基、ノルボルニレン基である。
Vは、一般式(LC1-1)~(LC1-16)のうちのいずれかで示される基を表す。
樹脂(A)は、極性基を有する有機基を含有する繰り返し単位、特に、極性基で置換された脂環炭化水素構造を有する繰り返し単位をさらに有することができる。
これにより基板密着性、現像液親和性が向上する。極性基で置換された脂環炭化水素構造の脂環炭化水素構造としてはアダマンチル基、ジアマンチル基、ノルボルナン基が好ましい。極性基としては水酸基、シアノ基が好ましい。
極性基を有する繰り返し単位の具体例を以下に挙げるが、本発明はこれらに限定されない。
このような繰り返し単位としては、例えば、下記一般式(4)で表される繰り返し単位が挙げられる。
反応溶媒としては、例えば、テトラヒドロフラン、1,4-ジオキサン、ジイソプロピルエーテルなどのエーテル類;メチルエチルケトン、メチルイソブチルケトンなどのケトン類;酢酸エチルなどのエステル溶媒;ジメチルホルムアミド、ジメチルアセトアミドなどのアミド溶剤;後述のプロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、シクロヘキサノンなどの感活性光線性又は感放射線性組成物を溶解する溶媒;等が挙げられる。より好ましくは感活性光線性又は感放射線性組成物に用いられる溶剤と同一の溶剤を用いて重合することが好ましい。これにより保存時のパーティクルの発生が抑制できる。
反応温度は、通常10℃~150℃であり、好ましくは30℃~120℃、さらに好ましくは60~100℃である。
精製は、水洗や適切な溶媒を組み合わせることにより残留単量体やオリゴマー成分を除去する液液抽出法、特定の分子量以下のもののみを抽出除去する限外ろ過等の溶液状態での精製方法や、樹脂溶液を貧溶媒へ滴下することで樹脂を貧溶媒中に凝固させることにより残留単量体等を除去する再沈殿法や、濾別した樹脂スラリーを貧溶媒で洗浄する等の固体状態での精製方法等の通常の方法を適用できる。
樹脂(A)の重量平均分子量の特に好ましい別の形態は、GPC法によるポリスチレン換算値で3,000~9,500である。重量平均分子量を3,000~9,500にすることにより、特にレジスト残渣(以降、「スカム」ともいう)が抑制され、より良好なパターンを形成することができる。
分散度(分子量分布)は、通常1~5であり、好ましくは1~3、更に好ましくは1.2~3.0、特に好ましくは1.2~2.0の範囲のものが使用される。分散度の小さいものほど、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、感活性光線性又は感放射線性組成物において、樹脂(A)は、1種で使用してもよいし、複数併用してもよい。
R61、R62及びR63は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基、又はアルコキシカルボニル基を表す。但し、R62はAr6と結合して環を形成していてもよく、その場合のR62は単結合又はアルキレン基を表す。
X6は、単結合、-COO-、又は-CONR64-を表す。R64は、水素原子又はアルキル基を表す。
L6は、単結合又はアルキレン基を表す。
Ar6は、(n+1)価の芳香環基を表し、R62と結合して環を形成する場合には(n+2)価の芳香環基を表す。
Y2は、n≧2の場合には各々独立に、水素原子又は酸の作用により脱離する基を表す。但し、Y2の少なくとも1つは、酸の作用により脱離する基を表す。
nは、1~4の整数を表す。
酸の作用により脱離する基Y2としては、下記一般式(VI-A)で表される構造がより好ましい。
Mは、単結合又は2価の連結基を表す。
Qは、アルキル基、ヘテロ原子を含んでいてもよいシクロアルキル基、ヘテロ原子を含んでいてもよいアリール基、アミノ基、アンモニウム基、メルカプト基、シアノ基又はアルデヒド基を表す。
Q、M、L1の少なくとも2つが結合して環(好ましくは、5員若しくは6員環)を形成してもよい。
Ar3は、芳香環基を表す。
R3は、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルコキシ基、アシル基又はヘテロ環基を表す。
M3は、単結合又は2価の連結基を表す。
Q3は、アルキル基、シクロアルキル基、アリール基又はヘテロ環基を表す。
Q3、M3及びR3の少なくとも二つが結合して環を形成してもよい。
R41、R42及びR43は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。R42はL4と結合して環を形成していてもよく、その場合のR42はアルキレン基を表す。
L4は、単結合又は2価の連結基を表し、R42と環を形成する場合には3価の連結基を表す。
R44及びR45は、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルコキシ基、アシル基又はヘテロ環基を表す。
M4は、単結合又は2価の連結基を表す。
Q4は、アルキル基、シクロアルキル基、アリール基又はヘテロ環基を表す。
Q4、M4及びR44の少なくとも二つが結合して環を形成してもよい。
R41、R42及びR43は、前述の一般式(V)中のR51、R52、R53と同義であり、また好ましい範囲も同様である。
L4は、前述の一般式(V)中のL5と同義であり、また好ましい範囲も同様である。
R44及びR45は、前述の一般式(3)中のR3と同義であり、また好ましい範囲も同様である。
M4は、前述の一般式(3)中のM3と同義であり、また好ましい範囲も同様である。
Q4は、前述の一般式(3)中のQ3と同義であり、また好ましい範囲も同様である。
Q4、M4及びR44の少なくとも二つが結合して形成される環としては、Q3、M3及びR3の少なくとも二つが結合して形成される環があげられ、また好ましい範囲も同様である。
以下に一般式(4)で表される繰り返し単位の具体例を示すが、本発明はこれに限定されるものではない。
R1は、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルキルオキシカルボニル基を表す。
R6及びR7は、それぞれ独立に、水素原子、ヒドロキシ基、炭素数1~10の直鎖状、分岐状又は環状のアルキル基、アルコキシ基又はアシロキシ基、シアノ基、ニトロ基、アミノ基、ハロゲン原子、エステル基(-OCOR又は-COOR:Rは炭素数1~6のアルキル基又はフッ素化アルキル基)、又はカルボキシル基を表す。
n3は0~6の整数を表す。
X4はメチレン基、酸素原子又は硫黄原子である。
一般式(V)又は一般式(VI)で表される繰り返し単位の具体例を下記に示すが、これらに限定されない。
感活性光線性又は感放射線性組成物は、活性光線又は放射線により酸を発生する化合物(以下、「光酸発生剤《PAG:Photo Acid Generator》」ともいう)を含有することが好ましい。
光酸発生剤は、低分子化合物の形態であっても良く、重合体の一部に組み込まれた形態であってもよい。また、低分子化合物の形態と重合体の一部に組み込まれた形態を併用してもよい。
光酸発生剤が、低分子化合物の形態である場合、分子量が3000以下であることが好ましく、2000以下であることがより好ましく、1000以下であることが更に好ましい。
光酸発生剤が、重合体の一部に組み込まれた形態である場合、樹脂(A)の一部に組み込まれても良く、樹脂(A)とは異なる樹脂に組み込まれてもよい。
本発明において、光酸発生剤が、低分子化合物の形態であることが好ましい。
光酸発生剤としては、公知のものであれば特に限定されないが、活性光線又は放射線、好ましくは電子線又は極紫外線の照射により、有機酸、例えば、スルホン酸、ビス(アルキルスルホニル)イミド、又はトリス(アルキルスルホニル)メチドの少なくともいずれかを発生する化合物が好ましい。
より好ましくは下記一般式(ZI)、(ZII)、(ZIII)で表される化合物を挙げることができる。
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、非求核性アニオン(求核反応を起こす能力が著しく低いアニオン)を表す。
各基が有するアリール基及び環構造については、置換基として更にアルキル基(好ましくは炭素数1~15)を挙げることができる。
また、ビス(アルキルスルホニル)イミドアニオンにおけるアルキル基は、互いに結合して環構造を形成してもよい。これにより、酸強度が増加する。
Xfは、それぞれ独立に、フッ素原子、又は少なくとも1つのフッ素原子で置換されたアルキル基を表す。
R1、R2は、それぞれ独立に、水素原子、フッ素原子、又は、アルキル基を表し、複数存在する場合のR1、R2は、それぞれ同一でも異なっていてもよい。
Lは、二価の連結基を表し、複数存在する場合のLは同一でも異なっていてもよい。
Aは、環状の有機基を表す。
xは1~20の整数を表し、yは0~10の整数を表し、zは0~10の整数を表す。
Xfのフッ素原子で置換されたアルキル基におけるアルキル基としては、好ましくは炭素数1~10であり、より好ましくは炭素数1~4である。また、Xfのフッ素原子で置換されたアルキル基は、パーフルオロアルキル基であることが好ましい。
Xfとして好ましくは、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の具体的としては、フッ素原子、CF3、C2F5、C3F7、C4F9、CH2CF3、CH2CH2CF3、CH2C2F5、CH2CH2C2F5、CH2C3F7、CH2CH2C3F7、CH2C4F9、CH2CH2C4F9が挙げられ、中でもフッ素原子、CF3が好ましい。
特に、双方のXfがフッ素原子であることが好ましい。
R1、R2としては、好ましくはフッ素原子又はCF3である。
yは0~4が好ましく、0がより好ましい。
zは0~5が好ましく、0~3がより好ましい。
Lの2価の連結基としては特に限定されず、―COO-、-OCO-、-CO-、-O-、-S―、-SO―、―SO2-、アルキレン基、シクロアルキレン基、アルケニレン基又はこれらの複数が連結した連結基などを挙げることができ、総炭素数12以下の連結基が好ましい。このなかでも―COO-、-OCO-、-CO-、-O-が好ましく、―COO-、-OCO-がより好ましい。
脂環基としては、単環でも多環でもよく、シクロペンチル基、シクロヘキシル基、シクロオクチル基などの単環のシクロアルキル基、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、アダマンチル基などの多環のシクロアルキル基が好ましい。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、アダマンチル基等の炭素数7以上のかさ高い構造を有する脂環基が、露光後加熱工程での膜中拡散性を抑制でき、MEEF(mask error enhancement factor)向上の観点から好ましい。
アリール基としては、ベンゼン環、ナフタレン環、フェナンスレン環、アントラセン環が挙げられる。
複素環基としては、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、ピリジン環由来のものが挙げられる。中でもフラン環、チオフェン環、ピリジン環由来のものが好ましい。
R201、R202及びR203のうち、少なくとも1つがアリール基であることが好ましく、三つ全てがアリール基であることがより好ましい。アリール基としては、フェニル基、ナフチル基などの他に、インドール残基、ピロール残基などのヘテロアリール基も可能である。R201~R203の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、炭素数3~10のシクロアルキル基を挙げることができる。アルキル基として、より好ましくはメチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基等を挙げることができる。シクロアルキル基として、より好ましくは、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロへプチル基等を挙げることができる。これらの基は更に置換基を有していてもよい。その置換基としては、ニトロ基、フッ素原子などのハロゲン原子、カルボキシル基、水酸基、アミノ基、シアノ基、アルコキシ基(好ましくは炭素数1~15)、シクロアルキル基(好ましくは炭素数3~15)、アリール基(好ましくは炭素数6~14)、アルコキシカルボニル基(好ましくは炭素数2~7)、アシル基(好ましくは炭素数2~12)、アルコキシカルボニルオキシ基(好ましくは炭素数2~7)等が挙げられるが、これらに限定されるものではない。
本発明においては、活性光線又は放射線の照射により以下に例示する酸を発生する光酸発生剤が好ましい。なお、例の一部には、体積の計算値を付記している(単位Å3)。なお、ここで求めた計算値は、アニオン部にプロトンが結合した酸の体積値である。
光酸発生剤の感活性光線性又は感放射線性組成物中の含有量は、組成物の全固形分を基準として、0.1~50質量%が好ましく、より好ましくは5~50質量%、更に好ましくは8~40質量%である。特に、電子線や極紫外線露光の際に高感度化、高解像性を両立するには光酸発生剤の含有率は高いほうが好ましく、更に好ましくは10~40質量%、最も好ましくは10~35質量%である。
上述した各成分を溶解させて感活性光線性又は感放射線性組成物を調製する際には、溶剤を使用できる。使用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、炭素数4~10の環状ラクトン、炭素数4~10の、環を含有してもよいモノケトン化合物、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。
アルキレングリコールモノアルキルエーテルとしては、例えば、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテルを好ましく挙げられる。
アルコキシプロピオン酸アルキルとしては、例えば、3-エトキシプロピオン酸エチル、3-メトキシプロピオン酸メチル、3-エトキシプロピオン酸メチル、3-メトキシプロピオン酸エチルを好ましく挙げられる。
アルコキシ酢酸アルキルとしては、例えば、酢酸-2-メトキシエチル、酢酸-2-エトキシエチル、酢酸-2-(2-エトキシエトキシ)エチル、酢酸-3-メトキシ-3-メチルブチル、酢酸-1-メトキシ-2-プロピルが好ましく挙げられる。
ピルビン酸アルキルとしては、例えば、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピルが好ましく挙げられる。
好ましく使用できる溶剤としては、常温常圧下で、沸点130℃以上の溶剤が挙げられる。具体的には、シクロペンタノン、γ-ブチロラクトン、シクロヘキサノン、乳酸エチル、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、3-エトキシプロピオン酸エチル、ピルビン酸エチル、酢酸-2-エトキシエチル、酢酸-2-(2-エトキシエトキシ)エチル、プロピレンカーボネートが挙げられる。
本発明に於いては、上記溶剤を単独で使用してもよいし、2種類以上を併用してもよい。
水酸基を含有する溶剤としては、例えば、エチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、乳酸エチル等を挙げることができ、これらの内でプロピレングリコールモノメチルエーテル、乳酸エチルが特に好ましい。
水酸基を含有しない溶剤としては、例えば、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、γ-ブチロラクトン、シクロヘキサノン、酢酸ブチル、N-メチルピロリドン、N,N-ジメチルアセトアミド、ジメチルスルホキシド等を挙げることができ、これらの内で、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、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)は、好ましくは1/99~99/1、より好ましくは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。
感活性光線性又は感放射線性組成物は、露光から加熱までの経時による性能変化を低減するために、(E)塩基性化合物を含有することが好ましい。
塩基性化合物としては、好ましくは、下記式(A)~(E)で示される構造を有する化合物を挙げることができる。
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。
また、アミン化合物は、アルキル鎖中に、酸素原子を有し、オキシアルキレン基が形成されていることが好ましい。オキシアルキレン基の数は、分子内に1つ以上、好ましくは3~9個、さらに好ましくは4~6個である。オキシアルキレン基の中でもオキシエチレン基(-CH2CH2O-)もしくはオキシプロピレン基(-CH(CH3)CH2O-もしくは-CH2CH2CH2O-)が好ましく、さらに好ましくはオキシエチレン基である。
アンモニウム塩化合物は、アルキル鎖中に、酸素原子を有し、オキシアルキレン基が形成されていることが好ましい。オキシアルキレン基の数は、分子内に1つ以上、好ましくは3~9個、さらに好ましくは4~6個である。オキシアルキレン基の中でもオキシエチレン基(-CH2CH2O-)もしくはオキシプロピレン基(-CH(CH3)CH2O-もしくは-CH2CH2CH2O-)が好ましく、さらに好ましくはオキシエチレン基である。
アンモニウム塩化合物のアニオンとしては、ハロゲン原子、スルホネート、ボレート、フォスフェート等が挙げられるが、中でもハロゲン原子、スルホネートが好ましい。ハロゲン原子としてはクロライド、ブロマイド、アイオダイドが特に好ましく、スルホネートとしては、炭素数1~20の有機スルホネートが特に好ましい。有機スルホネートとしては、炭素数1~20のアルキルスルホネート、アリールスルホネートが挙げられる。アルキルスルホネートのアルキル基は置換基を有していてもよく、置換基としては例えばフッ素、塩素、臭素、アルコキシ基、アシル基、アリール基等が挙げられる。アルキルスルホネートとして、具体的にはメタンスルホネート、エタンスルホネート、ブタンスルホネート、ヘキサンスルホネート、オクタンスルホネート、ベンジルスルホネート、トリフルオロメタンスルホネート、ペンタフルオロエタンスルホネート、ノナフルオロブタンスルホネート等が挙げられる。アリールスルホネートのアリール基としてはベンゼン環、ナフタレン環、アントラセン環が挙げられる。ベンゼン環、ナフタレン環、アントラセン環は置換基を有していてもよく、置換基としては炭素数1~6の直鎖若しくは分岐アルキル基、炭素数3~6のシクロアルキル基が好ましい。直鎖若しくは分岐アルキル基、シクロアルキル基として、具体的には、メチル、エチル、n-プロピル、イソプロピル、n-ブチル、i-ブチル、t-ブチル、n-ヘキシル、シクロヘキシル等が挙げられる。他の置換基としては炭素数1~6のアルコキシ基、ハロゲン原子、シアノ、ニトロ、アシル基、アシルオキシ基等が挙げられる。
本発明に係る組成物は、塩基性化合物として、プロトンアクセプター性官能基を有し、かつ、活性光線又は放射線の照射により分解してプロトンアクセプター性が低下、消失、又はプロトンアクセプター性から酸性に変化した化合物を発生する化合物〔以下、化合物(PA)ともいう〕を更に含んでいてもよい。
感活性光線性又は感放射線性組成物は、上記樹脂(A)とは別に疎水性樹脂(E)を有していてもよい。
疎水性樹脂はレジスト膜の表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、アウトガスの抑制などを挙げることができる。
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単環又は多環のシクロアルキル基であり、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アリール基としては、フェニル基、ナフチル基などのアリール基の少なくとも1つの水素原子がフッ素原子で置換されたものが挙げられ、更にフッ素原子以外の置換基を有していてもよい。
フッ素原子又は珪素原子を有する繰り返し単位の例としては、US2012/0251948A1の段落0519に例示されたものを挙げることが出来る。
ここで、疎水性樹脂中の側鎖部分が有するCH3部分構造には、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。
基板上に感活性光線性又は感放射線性組成物を塗布する方法としては、スピン塗布が好ましく、その回転数は1000~3000rpmが好ましい。
例えば、感活性光線性又は感放射線性組成物を精密集積回路素子の製造に使用されるような基板(例:シリコン/二酸化シリコン被覆)上にスピナー、コーター等の適当な塗布方法により塗布、乾燥し、レジスト膜を形成する。なお、予め公知の反射防止膜を塗設することもできる。また、トップコート層の形成前にレジスト膜を乾燥することが好ましい。
次いで、得られたレジスト膜上に、上記レジスト膜の形成方法と同様の手段によりトップコート組成物を塗布、乾燥し、トップコート層を形成することができる。
トップコート層を上層に有するレジスト膜に、通常はマスクを通して、電子線(EB)、X線又はEUV光を照射し、好ましくはベーク(加熱)を行い、現像する。これにより良好なパターンを得ることができる。
感活性光線性又は感放射線性組成物は、界面活性剤(F)を更に含んでいてもよい。界面活性剤を含有することにより、波長が250nm以下、特には220nm以下の露光光源を使用した場合に、良好な感度及び解像度で、密着性及び現像欠陥のより少ないパターンを形成することが可能となる。
界面活性剤としては、フッ素系及び/又はシリコン系界面活性剤を用いることが特に好ましい。
フッ素系及び/又はシリコン系界面活性剤としては、例えば、米国特許出願公開第2008/0248425号明細書の<0276>に記載の界面活性剤が挙げられる。また、エフトップEF301若しくはEF303(新秋田化成(株)製);フロラードFC430、431若しくは4430(住友スリーエム(株)製);メガファックF171、F173、F176、F189、F113、F110、F177、F120若しくはR08(DIC(株)製);サーフロンS-382、SC101、102、103、104、105若しくは106(旭硝子(株)製);トロイゾルS-366(トロイケミカル(株)製);GF-300若しくはGF-150(東亜合成化学(株)製)、サーフロンS-393(セイミケミカル(株)製);エフトップEF121、EF122A、EF122B、RF122C、EF125M、EF135M、EF351、EF352、EF801、EF802若しくはEF601((株)ジェムコ製);PF636、PF656、PF6320若しくはPF6520(OMNOVA社製);又は、FTX-204G、208G、218G、230G、204D、208D、212D、218D若しくは222D((株)ネオス製)を用いてもよい。なお、ポリシロキサンポリマーKP-341(信越化学工業(株)製)も、シリコン系界面活性剤として用いることができる。
また、米国特許出願公開第2008/0248425号明細書の<0280>に記載されているフッ素系及び/又はシリコン系以外の界面活性剤を使用してもよい。
感活性光線性又は感放射線性組成物は、溶解阻止化合物、染料、可塑剤、光増感剤、光吸収剤、及び/又は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、又はカルボキシ基を含んだ脂環族若しくは脂肪族化合物)を更に含んでいてもよい。
ここで「溶解阻止化合物」とは、酸の作用により分解して有機系現像液中での溶解度が減少する、分子量3000以下の化合物である。
感活性光線性又は感放射線性組成物、及び、本発明のパターン形成方法において使用される各種材料(例えば、本発明の処理液(例えば、現像液、リンス液)、レジスト溶剤、反射防止膜形成用組成物、トップコート形成用組成物など)は、金属、ハロゲンを含む金属塩、酸、アルカリ等の不純物を含まないことが好ましい。これら材料に含まれる不純物の含有量としては、1ppm以下が好ましく、1ppb以下がより好ましく、100ppt以下が更に好ましく、10ppt以下が特に好ましく、実質的に含まないこと(測定装置の検出限界以下であること)が最も好ましい。
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、ポリテトラフロロエチレン製、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、これらの材質とイオン交換メディアを組み合わせた複合材料であってもよい。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。
フィルター濾過の他、吸着材による不純物の除去を行っても良く、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。
現像液及びリンス液等の本発明の処理液としては、収容部を有する、化学増幅型レジスト膜のパターニング用処理液の収容容器に保存されたものを使用することが好ましい。この収容容器としては、例えば、収容部の、処理液に接触する内壁が、ポリエチレン樹脂、ポリプロピレン樹脂、及び、ポリエチレン-ポリプロピレン樹脂のいずれとも異なる樹脂、又は、防錆・金属溶出防止処理が施された金属から形成された、化学増幅型レジスト膜のパターニング用処理液の収容容器であることが好ましい。この収容容器の上記収容部に、化学増幅型レジスト膜のパターニング用処理液として使用される予定の有機溶剤を収容し、化学増幅型レジスト膜のパターニング時において、上記収容部から排出したものを使用することができる。
・Entegris社製 FluoroPurePFA複合ドラム(接液内面;PFA樹脂ライニング)
・JFE社製 鋼製ドラム缶(接液内面;燐酸亜鉛皮膜)
なお、後段の現像またはリンスで使用される処理液(表5に記載の処理液)に対して、アルカリ、ハロゲンを含む金属塩の定量分析を行った所、実質的にアルカリ、ハロゲンを含む金属塩が含まれないことが確認できた。
<樹脂(A)等>
(合成例1)樹脂(A-1)の合成
2Lフラスコにシクロヘキサノン600gを入れ、100mL/minの流量で一時間窒素置換した。その後、そこへ重合開始剤V-601(和光純薬工業(株)製)4.60g(0.02mol)を加え、内温が80℃になるまで昇温した。次に、以下のモノマーと重合開始剤V-601(和光純薬工業(株)製)4.60g(0.02mol)とを、シクロヘキサノン200gに溶解し、モノマー溶液を調製した。モノマー溶液を上記80℃に加熱したフラスコ中に6時間かけて滴下した。滴下終了後、更に80℃で2時間反応させた。
4-アセトキシスチレン 48.66g(0.3mol)
1-エチルシクロペンチルメタクリレート 109.4g(0.6mol)
モノマー1 22.2g(0.1mol)
表3において、樹脂の組成比(モル比)は、1H-NMR(核磁気共鳴)測定により算出した。樹脂の重量平均分子量(Mw:ポリスチレン換算)、分散度(Mw/Mn)はGPC(溶媒:THF)測定により算出した。
光酸発生剤としては、以下のものを用いた。
塩基性化合物としては、以下のものを用いた。
レジスト溶剤としては、以下のものを用いた。
C-1:プロピレングリコールモノメチルエーテルアセテート
C-2:プロピレングリコール
C-3:乳酸エチル
C-4:シクロヘキサノン
下記表4に示す各成分を、同表に示す溶剤に溶解させた。得られた溶液を0.03μmのポアサイズを有するポリエチレンフィルターを用いてろ過して、レジスト組成物を得た。
表4に記載の各レジスト組成物を用いて、以下の操作によりレジストパターンを形成した。
〔レジスト組成物の塗布及び塗布後ベーク(PB)〕
HMDS(ヘキサメチルジシラザン)処理を行った4インチシリコンウエハ上に、上記のようにして得られた各レジスト組成物を塗布し、90~120℃の条件で60秒間ベークし、膜厚40nmのレジスト膜を形成した。
上記のレジスト膜が形成されたウエハに、EUV露光装置を用いて、NA(レンズ開口数、Numerical Aperture)0.3とし、ダイポール照明でEUV露光を行った。具体的には、15~45nmのラインアンドスペースパターンを形成する為のパターンが含まれたマスクを介して、露光量を変えてEUV露光を行った。
露光後、EUV露光装置からウエハを取り出したら、ただちに、80~140℃の条件で60秒間ベークした。
その後、シャワー型現像装置(ACTES(株)製ADE3000S)を用いて、50回転(rpm)でウエハを回転しながら表5に記載の現像液(23℃)を、200mL/分の流量で、所定時間スプレー吐出して現像を行った。尚、表5中のS-1、S-2、S-5、S-6、及び、S-9を現像液として使用した。
表5中、「主成分」欄における数値はモル基準の混合比を意図する。
また、各処理液のリン原子を含む化合物の含有量は、JIS K0102:2013に規定された方法に基づき、全リンとして、吸光光度法により定量した。
その後、50回転(rpm)でウエハを回転しながら上記表5に記載のリンス液(23℃)を、200mL/分の流量で、所定時間スプレー吐出してリンス処理を行った。
最後に、2500回転(rpm)で60秒間高速回転してウエハを乾燥させた。尚、表5中のS-3、S-4、S-7、S-8、S-10~S-13、SA-1、及び、SA-2をリンス液として使用した。
以下の項目について、レジストパターンの評価を行った。結果の詳細は表6に示す。
得られたレジストパターンを、走査型電子顕微鏡((株)日立製作所製S-9380II)を用いて観察した。30nmの線幅において、ラインとスペースとの比率が1:1で分離解像する照射エネルギーを感度(mJ/cm2)とした。
45nm~15nmの解像状況を走査型電子顕微鏡((株)日立製作所製S-9380II)を用いて観察し、1:1のラインアンドスペースが問題なく解像しているものを限界解像の値とした。
上記の方法にて得られた線幅30nmの解像状況及びパターン形状を、走査型電子顕微鏡((株)日立製作所製S-9380II)によって観察して、残渣欠陥の個数を求めた。観察箇所を1ミクロンずつずらしながら、1000枚の写真撮影を行い、パターン上に確認された残渣欠陥の個数をカウントした。残渣欠陥の個数が小さいほど性能が良好であることを示す。
(表中の評価結果と残渣欠陥の個数の関係)
A:0個
B:1~4個
C:5~9個
D:10~19個
E:20個以上
<EB露光評価>
上記表4に記載のレジスト組成物を用いて、以下の操作によりレジストパターンを形成した。
6インチシリコンウエハ上に有機膜形成用組成物DUV44(Brewer Science社製)を塗布し、200℃で60秒間ベークして、膜厚60nmの有機膜を形成した。その上に表7に記載のレジスト組成物を塗布し、90~120℃の条件で60秒間ベークし、膜厚40nmのレジスト膜を形成した。
上記のレジスト膜を形成したウエハに、電子線照射装置((株)JEOL製 JBX6000FS/E;加速電圧50keV)を用いて、1.25nm刻みで20nm~17.5nmのラインアンドスペースパターン(長さ方向0.12mm、描画本数20本)を、露光量を変えて露光した。
露光後、電子線照射装置からウエハを取り出したら、ただちに、80~140℃の条件で60秒の条件でホットプレート上にて加熱した。
シャワー型現像装置(ACTES(株)製ADE3000S)を用いて、50回転(rpm)でウエハを回転しながら上記表5に記載の現像液(23℃)を、200mL/分の流量で、所定時間スプレー吐出して現像を行った。尚、表5中のS-1、S-2、S-5、S-6、及び、S-9を現像液として使用した。
表5中、「主成分」欄における数値はモル基準の混合比を意図する。
その後、50回転(rpm)でウエハを回転しながら表5に記載のリンス液(23℃)を、200mL/分の流量で、所定時間スプレー吐出してリンス処理を行った。
最後に、2500回転(rpm)で60秒間高速回転してウエハを乾燥させた。尚、表5中のS-3、S-4、S-7、S-8、S-10~S-13、SA-1、及び、SA-2をリンス液として使用した。
上記表6および表7に示す通り、いずれの露光光源を用いた場合においても、現像液及びリンス液の少なくとも一方の処理液中の硫黄含有化合物の含有量が少ないと、欠陥残渣が少ないことがわかった(実施例参照)。
一方、現像液及びリンス液の少なくとも一方の処理液中に硫黄含有化合物の含有量が少ないものを用いなければ、欠陥残渣が増加することがわかった(比較例参照)。
このように、現像液及びリンス液の少なくとも一方の処理液中に硫黄含有化合物の含有量が少ないものを用いなければ、欠陥残渣が増加して、感度や限界解像等のパターン性能に悪影響を及ぼすことが示された。
Claims (12)
- 感活性光線又は感放射線性組成物から得られるレジスト膜を、現像及び洗浄の少なくとも一方を行うために使用され、有機溶剤を含有するレジスト膜パターニング用の処理液であって、
前記処理液中、硫黄原子を含む化合物の含有量が10mmol/L以下である、処理液。 - 前記処理液が、現像液である、請求項1に記載の処理液。
- 前記有機溶剤が、エステル系溶剤を含む、請求項2に記載の処理液。
- 前記エステル系溶剤が、酢酸ブチル、酢酸アミル、酢酸イソアミル、酢酸2-メチルブチル、酢酸1-メチルブチル、酢酸ヘキシル、プロピオン酸ペンチル、プロピオン酸ヘキシル、プロピオン酸ヘプチル及びブタン酸ブチルからなる群から選ばれる少なくともいずれか1種を含む、請求項3に記載の処理液。
- 前記処理液が、リンス液である、請求項1に記載の処理液。
- 前記有機溶剤が、炭化水素系溶剤を含む、請求項5に記載の処理液。
- 前記有機溶剤が、炭素数5以上の炭化水素系溶剤を含む、請求項6に記載の処理液。
- 前記炭化水素系溶剤が、ウンデカンを含む、請求項6又は7に記載の処理液。
- 前記処理液中、さらに、リン原子を含む化合物の含有量が10mmol/L以下である、請求項1~8のいずれか1項に記載の処理液。
- 前記硫黄原子を含む化合物の沸点が190℃以上である、請求項1~9のいずれか1項に記載の処理液。
- 感活性光線又は感放射線性組成物を用いてレジスト膜を形成するレジスト膜形成工程と、
前記レジスト膜を露光する露光工程と、
露光された前記レジスト膜を請求項1、2、3、4、9又は10に記載の処理液によって処理する処理工程と、
を含む、パターン形成方法。 - 前記処理工程は、リンス液によって洗浄するリンス工程を備え、
前記リンス液が請求項1、5、6、7、8、9又は10に記載の処理液である、請求項11に記載のパターン形成方法。
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WO2019125689A1 (en) * | 2017-12-22 | 2019-06-27 | Illumina, Inc. | Light detection devices with protective liner and methods related to same |
US11256033B2 (en) | 2017-12-22 | 2022-02-22 | Illumina, Inc. | Two-filter light detection devices and methods related to same |
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JP7084985B2 (ja) * | 2018-04-19 | 2022-06-15 | 富士フイルム株式会社 | パターンの製造方法、光学フィルタの製造方法、固体撮像素子の製造方法、画像表示装置の製造方法、光硬化性組成物および膜 |
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