WO2011145663A1 - 液浸上層膜形成用組成物及びフォトレジストパターン形成方法 - Google Patents
液浸上層膜形成用組成物及びフォトレジストパターン形成方法 Download PDFInfo
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- WO2011145663A1 WO2011145663A1 PCT/JP2011/061459 JP2011061459W WO2011145663A1 WO 2011145663 A1 WO2011145663 A1 WO 2011145663A1 JP 2011061459 W JP2011061459 W JP 2011061459W WO 2011145663 A1 WO2011145663 A1 WO 2011145663A1
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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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
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
- C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
Definitions
- the present invention relates to a composition for forming a liquid immersion upper layer film and a method for forming a photoresist pattern.
- Stepper type or step-and-scan type projection exposure apparatus for transferring a reticle pattern as a photomask to each shot region via a projection optical system on a wafer coated with a photoresist film in the manufacture of a semiconductor element or the like Is used.
- the resolution of the projection optical system provided in the projection exposure apparatus becomes higher as the exposure wavelength used is shorter and the numerical aperture of the projection optical system is larger. For this reason, along with the miniaturization of integrated circuits, the exposure wavelength used in the projection exposure apparatus has become shorter, and the numerical aperture of the projection optical system has also increased.
- the depth of focus is important as well as the resolution.
- the resolution R and the depth of focus ⁇ are expressed by the following equations, respectively.
- a larger depth of focus ⁇ can be obtained by using short-wavelength radiation.
- NA is the numerical aperture of the projection optical system
- k1 and k2 are process coefficients.
- the space in which the wafer is disposed is filled with air or nitrogen.
- the refractive index n in water of light having a wavelength of 193 nm is 1.44, and the resolution R is compared with that during exposure using air or nitrogen as a medium. 69.4% and the depth of focus is 144%.
- Such an exposure method using a medium is called an immersion exposure method, which can shorten the wavelength of radiation and transfer a finer pattern (see JP-A-11-176727).
- the photoresist film formed on the wafer and the lens of the projection exposure apparatus come into contact with water, respectively, so that the water penetrates into the photoresist film and the resolution of the photoresist is reduced. May decrease. Further, the components of the photoresist composition may elute into water, which may contaminate the lens surface of the projection exposure apparatus.
- a method of forming a liquid immersion upper layer film as a protective film on the photoresist film for the purpose of blocking the photoresist film from a medium such as water.
- This immersion upper layer has sufficient permeability to the wavelength of radiation, can be formed on the photoresist film while suppressing intermixing with the photoresist film, and is eluted in a medium such as water. It is generally required that a stable coating film can be maintained without being dissolved, and that it is hardly soluble in an alkali solution or the like as a developing solution (Japanese Patent Laid-Open Nos. 2005-264131 and 2006-64711). Gazette and JP-A-2008-139789).
- the present invention has been made based on the above circumstances, has moderate water repellency and high solubility in a developer, and has a watermark defect, a bridge defect, etc. even when the scanning speed is high.
- An object of the present invention is to provide a composition for forming a liquid immersion upper film capable of forming a liquid immersion upper film capable of suppressing the occurrence of various defects.
- a composition having a structural unit (I) represented by the following formula (1) (hereinafter also referred to as “[A] polymer”), and [S] a composition for forming an immersion upper layer film containing a solvent It is a thing.
- R 1 is a hydrogen atom, a methyl group or a trifluoromethyl group.
- the polymer preferably further has a structural unit (II) having a sulfo group.
- the polymer preferably further has a structural unit (III) represented by the following formula (3).
- R 2 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
- R 3 represents a linear or branched monovalent hydrocarbon group having 1 to 12 carbon atoms, or a carbon atom.
- the polymer preferably further has a structural unit (IV) represented by the following formula (4).
- R 4 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
- R 5 represents a linear or branched monovalent hydrocarbon group having 1 to 12 carbon atoms, or a carbon atom. (This is a monovalent alicyclic group of formula 3 to 20.)
- composition for forming a liquid immersion upper layer film has a polymer (B, “B” structural unit (I) and structural unit (III), and a higher fluorine atom content than [A] polymer (hereinafter referred to as “[ B] polymer ” It is preferable to further contain.
- the polymer preferably further has a structural unit (IV).
- the photoresist pattern forming method of the present invention comprises: (1) A step of applying a photoresist composition on a substrate to form a photoresist film, (2) forming a liquid immersion upper film by applying the liquid immersion upper film forming composition on the photoresist film; (3) a step of disposing an immersion medium between the immersion upper layer film and the lens and exposing the photoresist film and the upper layer film through the immersion medium and a mask having a predetermined pattern; (4) A step of developing the exposed photoresist film and upper layer film.
- the composition for forming a liquid immersion upper layer film according to the present invention has moderate water repellency and high solubility in a developer, and even if the scanning speed is high, watermark defects and bridge defects. It is possible to form a liquid immersion upper layer film that can suppress the occurrence of various defects such as the above.
- FIG. 3 is a schematic diagram showing a state in which an 8-inch silicon wafer is placed on a silicon rubber sheet so that ultrapure water does not leak in measurement of the elution amount of the upper layer film formed by the composition for forming an immersion upper layer film of the present invention. . It is sectional drawing in the measurement state of the elution amount of the upper film formed with the composition for liquid immersion upper film formation of this invention.
- composition for forming a liquid immersion upper layer film of the present invention is used for forming a liquid immersion upper film on the surface of a photoresist film formed by the photoresist composition, comprising [A] a polymer and [S] Contains a solvent.
- the said composition for liquid immersion upper layer film formation may contain a [B] polymer as a suitable component.
- the said composition for liquid immersion upper layer film formation may contain another polymer and another arbitrary component, unless the effect of this invention is impaired.
- each component will be described in detail.
- the polymer has the structural unit (I) represented by the above formula (1).
- the composition for forming a liquid immersion upper layer film contains the [A] polymer having the structural unit (I)
- the formed liquid immersion upper layer film has an appropriate water repellency and dissolves in the developer.
- it protects the photoresist film during immersion exposure, maintains a stable coating without leaching into a medium such as water, and eliminates defects such as watermark defects, bubble defects, pattern defects, and bridge defects. Generation
- production can be suppressed effectively and a high-resolution resist pattern can be formed.
- the [A] polymer further has structural unit (II), structural unit (III), and structural unit (IV).
- the [A] polymer may have 2 or more types of each structural unit.
- each structural unit will be described in detail.
- the structural unit (I) is represented by the above formula (1).
- R ⁇ 1 > is a hydrogen atom, a methyl group, or a trifluoromethyl group.
- (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-butyl) ester is preferred.
- the content of the structural unit (I) in the [A] polymer is preferably 20 mol% to 99 mol% with respect to the total structural unit of the [A] polymer.
- the structural unit (II) is a structural unit having a sulfo group.
- Examples of the structural unit (II) include structural units represented by the following formulas (2-1) and (2-2).
- R 6 and R 7 are each independently a hydrogen atom, a methyl group or a trifluoromethyl group.
- R 8 and R 9 are each independently a single bond, a linear or branched divalent hydrocarbon group having 1 to 6 carbon atoms, a divalent alicyclic group having 4 to 12 carbon atoms, or carbon It is a bivalent aromatic hydrocarbon group of formula 6-12.
- Examples of the linear or branched divalent hydrocarbon group having 1 to 6 carbon atoms represented by R 8 and R 9 include, for example, a methylene group, an ethylene group, a 1,3-propylene group, 1,2- Propylene group, tetramethylene group, pentamethylene group, hexamethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1- Examples thereof include a methyl-1,4-butylene group and a 2-methyl-1,4-butylene group.
- Examples of the divalent alicyclic group having 4 to 12 carbon atoms represented by R 8 and R 9 include a monocyclic hydrocarbon group and a bridged cyclic hydrocarbon group.
- Examples of the monocyclic hydrocarbon group include a cyclobutylene group such as a 1,3-cyclobutylene group, a cyclopentylene group such as a 1,3-cyclopentylene group, and a cyclohexylene group such as a 1,4-cyclohexylene group. 1,5-cyclooctylene group and the like.
- bridged cyclic hydrocarbon group examples include norbornylene groups such as 1,4-norbornylene group and 2,5-norbornylene group, adamantylene groups such as 1,5-adamantylene group, 2,6-adamantylene group and the like. Can be mentioned.
- Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms represented by R 8 and R 9 include a phenylene group and a tolylene group.
- R 8 in the above formula (2-1) is a single bond, a linear or branched divalent hydrocarbon group having 1 to 6 carbon atoms, or a divalent aromatic hydrocarbon having 6 to 12 carbon atoms.
- a single bond, a methylene group, and a phenylene group are more preferable.
- R 9 in the above formula (2-2) is preferably a linear or branched divalent hydrocarbon group having 1 to 6 carbon atoms, more preferably a 2-methylpropane-2,3-diyl group.
- the structural unit (II) is preferably a structural unit represented by the following formula.
- R 7 has the same meaning as in the above formula (2-2).
- the content of the structural unit (II) in the [A] polymer is preferably 1 mol% to 20 mol% with respect to all the structural units of the [A] polymer.
- the structural unit (III) is represented by the above formula (3).
- R 2 is a hydrogen atom, a methyl group or a trifluoromethyl group.
- R 3 is a linear or branched monovalent hydrocarbon group having 1 to 12 carbon atoms or a monovalent alicyclic group having 3 to 20 carbon atoms. However, at least one of the hydrogen atoms of the hydrocarbon group and alicyclic group is substituted with a fluorine atom.
- Examples of the structural unit (III) include a structural unit described in JP-A-2007-304537, a structural unit described in JP-A-2008-088343, and a structural unit represented by the following formula.
- R ⁇ 2 > is synonymous with the said Formula (3).
- Monomers that give structural unit (III) include trifluoromethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, Fluoro n-propyl (meth) acrylic acid ester, perfluoro i-propyl (meth) acrylic acid ester, perfluoro n-butyl (meth) acrylic acid ester, perfluoro i-butyl (meth) acrylic acid ester, perfluoro t -Butyl (meth) acrylic acid ester, 2- (1,1,1,3,3,3-hexafluoropropyl) (meth) acrylic acid ester, 1- (2,2,3,3,4,4,4) 5,5-octafluoropentyl) (meth) acrylic acid ester, perfluorocyclohexylmethyl (meth) acrylic Acid ester, 1- (2,2,3,3,3-pentafluoropropyl) (meth
- the content of the structural unit (III) in the [A] polymer is preferably 5 mol% to 70 mol% with respect to all the structural units of the [A] polymer.
- the structural unit (IV) is represented by the above formula (4).
- R 4 is a hydrogen atom, a methyl group or a trifluoromethyl group.
- R 5 is a linear or branched monovalent hydrocarbon group having 1 to 12 carbon atoms or a monovalent alicyclic group having 3 to 20 carbon atoms.
- R 5 examples include methyl group, ethyl group, 1,3-propyl group, 1,2-propyl group, tetramethyl group, pentamethyl group, hexamethyl group, heptamethyl group, octamethyl group, nonamethyl group, decamethyl group, 1- Methyl-1,3-propyl group, 2-methyl-1,3-propyl group, 2-methyl-1,2-propyl group, 1-methyl-1,4-butyl group, 2-methyl-1,4-butyl Group, methylidene group, ethylidene group, propylidene group, 2-propylidene group, 1,3-cyclobutyl group, 1,3-cyclopentyl group, 1,4-cyclohexyl group, 1,5-cyclooctyl group, 1,4-norbornyl Group, 2,5-norbornyl group, 1,5-adamantyl group and 2,6-adamantyl group are preferable.
- Examples of the monomer that gives the structural unit (IV) include methyl methacrylate, ethyl methacrylate, butyl methacrylate, pentyl methacrylate, cyclohexyl methacrylate, adamantyl methacrylate, and dicyclopentyl methacrylate.
- the content of the structural unit (IV) in the [A] polymer is preferably 5 mol% to 55 mol% with respect to all the structural units of the [A] polymer.
- the polymer may have a structural unit (V) as another structural unit as long as the effects of the present invention are not impaired.
- Examples of the structural unit (V) include structural units represented by the following formulas (5-1) and (5-2).
- R 10 and R 11 are a hydrogen atom, a methyl group or a trifluoromethyl group.
- R 12 represents a single bond, a linear or branched alkanediyl group having 1 to 6 carbon atoms (excluding 1,2-ethylene group), and a divalent alicyclic group having 4 to 12 carbon atoms. is there.
- R 13 is a single bond, a linear or branched alkanediyl group having 1 to 6 carbon atoms, or a divalent alicyclic group having 4 to 12 carbon atoms.
- R 14 is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, or a monovalent alicyclic group having 3 to 10 carbon atoms. However, at least one of the hydrogen atoms of the hydrocarbon group and alicyclic group is substituted with a fluorine atom.
- R 12 and R 13 are methylene group, 1,1-ethylene group, 1,3-propylene group, 1,2-propylene, tetramethylene group, pentamethylene group, hexamethylene group, 1-methyl-1, 3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl-1,4-butylene group, 2-methyl-1,4-butylene group, 1, 3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene group, 1,5-cyclooctylene group, 1,4-norbornylene group, 2,5-norbornylene group, 1,5-adamantylene And the group 2,6-adamantylene is preferred.
- R 12 contains a divalent alicyclic group, it is preferable to insert an alkanediyl group having 1 to 4 carbon atoms as a spacer between the bistrifluoromethyl-hydroxy-methyl group and the aliphatic cyclic hydrocarbon group.
- R 12 is preferably a hydrocarbon group containing a 2,5-norbornylene group or a propylene group.
- R 14 is preferably a trifluoromethyl group.
- Monomers that give the structural unit (V) include (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-3-propyl) ester, (meth) acrylic acid ( 1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-pentyl) ester, (meth) acrylic acid 2- ⁇ [5- (1 ′, 1 ′, 1′-trifluoro-2 '-Trifluoromethyl-2'-hydroxy) propyl] bicyclo [2.2.1] heptyl ⁇ ester, (meth) acrylic acid 3- ⁇ [8- (1', 1 ', 1'-trifluoro-2 '-Trifluoromethyl-2'-hydroxy) propyl] tetracyclo [6.2.1.13,6.02,7] dodecyl ⁇ ester, (((trifluoromethyl) sulfonyl) amino) ethyl-1-meta Relate, 2 - (((trifluoromethyl) sulf
- the content of the [A] polymer in the composition for forming a liquid immersion upper layer film is preferably 20% by mass or more, more preferably 40% by mass, when the total of all polymer components is 100% by mass. 60 mass% or more is especially preferable. [A] If the content of the polymer is less than 20% by mass, various defects may occur.
- the composition for forming a liquid immersion upper layer film has at least one structural unit selected from the group consisting of the structural unit (I) and the structural unit (V), and the structural unit (III), and [ A] It is preferable to further contain a [B] polymer having a higher fluorine atom content than the polymer.
- the [B] polymer has a higher water atom repellency than the [A] polymer because it has a higher fluorine atom content than the [A] polymer.
- the liquid immersion upper layer film forming composition further contains the [B] polymer, the [B] polymer is unevenly distributed in the surface layer portion with respect to the [A] polymer, and the receding contact angle is lowered. Without this, it is possible to prevent watermark defects caused by the remaining droplets.
- the polymer preferably further has the structural unit (IV) described above.
- the structural units (I), (III), (IV) and (V) the contents described in the section of [A] polymer can be applied.
- the [B] polymer may have 2 or more types of each structural unit.
- the content of at least one structural unit selected from the group consisting of the structural unit (I) and the structural unit (V) in the polymer is 20 moles relative to the total structural unit of the [B] polymer. % To 80 mol% is preferred.
- the content of the structural unit (III) in the polymer is preferably 5 mol% to 80 mol% with respect to the total structural unit of the [B] polymer.
- the content of the structural unit (IV) in the polymer is preferably 5 mol% to 55 mol%, more preferably 5 mol% to 50 mol%, based on all the structural units of the [B] polymer. .
- the content of the [B] polymer in the composition for forming a liquid immersion upper layer film is preferably 60% by mass or less, more preferably 50% by mass, when the total of all polymer components is 100% by mass. 40 mass% or more is especially preferable. [B] If the polymer content exceeds 60% by mass, various defects may occur.
- the composition for forming a liquid immersion upper layer film may contain another polymer other than the above-mentioned [A] polymer and [B] polymer as long as the effects of the present invention are not impaired.
- Other polymer embodiments include: (I) a polymer having structural unit (V) and structural unit (II); (Ii) The polymer etc. which have the structural unit (VI) and structural unit (II) which are mentioned later are mentioned. For the details of the structural unit (II) and the structural unit (V), the contents described in the section [A] Polymer can be applied.
- the content of the structural unit (V) in the polymer (i) is preferably 20 mol% to 99 mol%, more preferably 30 mol% to 99 mol%, based on all the structural units of the polymer (i). preferable.
- bridging defect can be suppressed by making the content rate of a structural unit (V) into the said specific range.
- the content of the structural unit (II) in the polymer (i) is preferably 1 mol% to 20 mol%, more preferably 1 mol% to 15 mol%, based on all the structural units of the polymer (i). preferable. By setting the content of the structural unit (II) within the specific range, the occurrence of blob defects can be suppressed.
- structural unit (VI) Examples of the structural unit (VI) include structural units represented by the following formula (6-1), formula (6-2), and formula (6-3).
- R 15 , R 16 and R 17 are each independently a hydrogen atom, a methyl group or a trifluoromethyl group.
- R 18 , R 19 and R 20 are each independently a linear or branched divalent hydrocarbon group having 1 to 6 carbon atoms or a divalent alicyclic group having 4 to 12 carbon atoms. .
- Examples of the linear or branched divalent hydrocarbon group having 1 to 6 carbon atoms represented by R 18 , R 19 and R 20 include, for example, ethylene group, 1,3-propylene group, 1,2- Propylene, tetramethylene group, pentamethylene group, hexamethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl -1,4-butylene group, 2-methyl-1,4-butylene group and the like.
- Examples of the divalent alicyclic group having 4 to 12 carbon atoms represented by R 18 , R 19 and R 20 include an arylene group such as a phenylene group and a tolylene group, and a cyclohexane such as a 1,3-cyclobutylene group.
- Butylene group such as 1,3-cyclopentylene group, cyclohexylene group such as 1,4-cyclohexylene group, cyclooctylene group such as 1,5-cyclooctylene group, 1,4- Examples thereof include norbornylene groups such as norbornylene group and 2,5-norbornylene group, and adamantylene groups such as 1,5-adamantylene group and 2,6-adamantylene group.
- Examples of the monomer giving the structural unit (VI) include 2-methacryloyloxyethyl hexahydrophthalate, 3-methacryloyloxypropyl hexahydrophthalate, 4-methacryloyloxybutyl hexahydrophthalate, 2-cyclohexacarboxylic acid 2- Examples include methacryloyloxy, 3-methacryloyloxy propylcarboxylate, and (meth) acrylic acid.
- composition for forming a liquid immersion upper layer film contains the polymer (ii) having the structural unit (VI), blob defects can be further suppressed.
- the content of the structural unit (VI) in the polymer (ii) is preferably 20 mol% to 99 mol%, more preferably 30 mol% to 99 mol%, based on all structural units of the polymer (ii). preferable. If the content of the structural unit (VI) is less than 20 mol%, the solubility in an alkali developer deteriorates and the number of undissolved defects tends to increase, and if it exceeds 99 mol%, the solubility in a solvent deteriorates. There is a fear.
- the content of the structural unit (II) in the polymer of (ii) is preferably 1 mol% to 20 mol%, more preferably 1 mol% to 15 mol%, based on all the structural units of the polymer of (ii). preferable.
- a blob defect can be suppressed by making the content rate of structural unit (II) into the said specific range.
- Examples of the monomer that gives a structural unit that other polymers other than the above (i) to (ii) may have include dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; phenyl (Meth) acrylic acid aryl esters such as (meth) acrylate and benzyl (meth) acrylate; aromatic vinyls such as styrene, ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene Nitrile group-containing radical polymerizable monomers such as acrylonitrile and methacrylonitrile; Amide bond-containing radical polymerizable monomers such as acrylamide and methacrylamide; Fatty acid vinyls such as vinyl acetate; Chlorine such as vinyl chloride and vinylidene chloride Containing radical polymerizable monomer; 1,
- Each polymer can be synthesized, for example, by radical polymerization of monomers that give each structural unit in a polymerization solvent in the presence of a polymerization initiator or a chain transfer agent.
- polymerization solvent examples include alcohols, cyclic ethers, alkyl ethers of polyhydric alcohols, alkyl ether acetates of polyhydric alcohols, aromatic hydrocarbons, ketones, and esters.
- cyclic ethers, alkyl ethers of polyhydric alcohols, alkyl ether acetates of polyhydric alcohols, ketones, esters and the like can be mentioned.
- the polystyrene-reduced weight average molecular weight (Mw) of each polymer by gel permeation chromatography (GPC) is preferably 2,000 to 100,000, more preferably 2,500 to 50,000.
- Mw weight average molecular weight
- the molecular weight distribution (Mw / Mn) of each polymer is preferably 1 to 5, more preferably 1 to 3.
- the polymer component contained in the composition for forming a liquid immersion upper layer film can form a liquid immersion upper layer film that is stable with respect to the liquid immersion liquid upon irradiation, and development for forming a resist pattern. It is a resin that can be dissolved in a liquid.
- stable against immersion liquid means that the rate of change of the film thickness measured as a result of the stability evaluation test is within 3% of the initial film thickness.
- a coating / developer (CLEAN TRACK ACT8, manufactured by Tokyo Electron) is used to spin coat the composition for forming an upper liquid immersion film on an 8-inch silicon wafer, and pre-bake at 90 ° C. for 60 seconds.
- a liquid immersion upper layer film having a thickness of 90 nm is formed.
- the initial film thickness of the immersion upper film is measured using an optical interference type film thickness measuring device (Lambda Ace VM-2010, manufactured by Dainippon Screen Mfg. Co., Ltd.).
- the wafer is spun off at a rotational speed of 4,000 rpm for 15 seconds and spin-dried.
- the film thickness of the upper film is measured again, and the change in the film thickness of the upper film is calculated.
- the ratio of the reduced film thickness to the initial film thickness is within 3%, it is evaluated as “stable against immersion liquid”. Further, “dissolved in a developing solution” after forming a resist pattern means that the upper layer film is removed without any residue on the resist pattern after development using an alkaline aqueous solution.
- the composition for forming a liquid immersion upper layer film of the present invention contains an [S] solvent for the purpose of dissolving the polymer component.
- [S] As the solvent, a solvent that does not deteriorate the lithography performance such as causing intermixing with the photoresist film when applied onto the photoresist film is preferable.
- Solvents include, for example, monohydric alcohols, polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol alkyl ether acetates, ethers, cyclic ethers, higher hydrocarbons, aromatics Examples thereof include hydrocarbons, ketones, esters, water and the like.
- Examples of monovalent alcohols include 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, tert-amyl alcohol, and neopentyl alcohol.
- polyhydric alcohols examples include ethylene glycol and propylene glycol.
- polyhydric alcohol alkyl ethers examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl.
- examples include ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and ethylene glycol monoisobutyl ether.
- polyhydric alcohol alkyl ether acetates examples include ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate.
- ethers include dipropyl ether, diisopropyl ether, butyl methyl ether, butyl ethyl ether, butyl propyl ether, dibutyl ether, diisobutyl ether, tert-butyl methyl ether, tert-butyl ethyl ether, tert-butyl propyl ether, Di-tert-butyl ether, dipentyl ether, diisoamyl ether, cyclopentyl methyl ether, cyclohexyl methyl ether, cyclopentyl ethyl ether, cyclohexyl ethyl ether, cyclopentyl propyl ether, cyclopentyl-2-propyl ether, cyclohexyl propyl ether, cyclohexyl-2-propyl ether , Cyclopentyl butyl ether, cyclopent
- cyclic ethers examples include tetrahydrofuran and dioxane.
- Examples of higher hydrocarbons include decane, dodecane, and undecane.
- aromatic hydrocarbons examples include benzene, toluene, xylene and the like.
- ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, diacetone alcohol, and the like.
- esters examples include ethyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 -Methyl hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate and the like.
- monohydric alcohols ethers, cyclic ethers, polyhydric alcohol alkyl ethers, polyhydric alcohol alkyl ether acetates, and higher hydrocarbons are preferred.
- composition for forming a liquid immersion upper layer film may contain other surfactants and the like for the purpose of improving coating properties, antifoaming properties, leveling properties, etc. These optional components can also be blended.
- surfactants include, for example, BM-1000, BM-1100 (above, manufactured by BM Chemie), MegaFuck F142D, F172, F173, F173 (above, manufactured by Dainippon Ink and Chemicals), Florard FC -135, FC-170C, FC-430, FC-431 (manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145 ( Asahi Glass, SH-28PA, -190, -193, SZ-6032, SF-8428 (above Toray Dow Corning Silicone), Emulgen A-60, 104P, 306P (above, Kao) etc. Is mentioned.
- As a compounding quantity of surfactant 5 mass% or less is preferable with respect to 100 mass% of total amounts of a polymer component.
- Surfactants may be used alone or in admixture of two or more.
- composition for forming a liquid immersion upper layer film is dissolved or dispersed by mixing the [A] polymer in the [S] solvent, and if necessary, the [B] polymer, other polymers, and other optional components.
- the said composition for liquid immersion upper layer film formation can be prepared by filtering the solution prepared so that total solid content may become a desired value with a filter with a hole diameter of about 200 nm.
- the solid content concentration is not particularly limited, but is usually 0.1% by mass to 20.0% by mass.
- the said composition for liquid immersion upper layer film formation is so preferable that there are few impurities, such as a halogen ion and a metal.
- impurities such as a halogen ion and a metal.
- membrane and the uniform solubility to an alkali developing solution can be improved more.
- the purification method of the polymer component include chemical purification methods such as washing with water and liquid-liquid extraction, and combinations of these chemical purification methods with physical purification methods such as ultrafiltration and centrifugation.
- a step of applying a photoresist composition on a substrate to form a photoresist film (2) forming a liquid immersion upper film by applying the liquid immersion upper film forming composition on the photoresist film; (3) a step of disposing an immersion medium between the immersion upper layer film and the lens and exposing the photoresist film and the upper layer film through the immersion medium and a mask having a predetermined pattern; (4) A step of developing the exposed photoresist film and upper layer film.
- the formation method it has sufficient transparency especially for exposure wavelengths of 248 nm (KrF) and 193 nm (ArF), can suppress intermixing with a photoresist film, and is extremely eluted in a medium such as water during immersion exposure.
- This step is a step of forming a photoresist film by applying a photoresist composition on a substrate.
- a photoresist composition As the substrate, a silicon wafer, a silicon wafer coated with aluminum, or the like is usually used.
- it is also preferable to previously form an organic or inorganic antireflection film on the surface of the substrate see, for example, Japanese Patent Publication No. 6-12452.
- the photoresist composition is not particularly limited and can be appropriately selected according to the intended use of the resist, but a chemically amplified positive resist material containing an acid generator is preferred.
- the chemically amplified positive resist material include a radiation sensitive polymer composition containing an acid dissociable group-modified alkali-soluble resin and a radiation sensitive acid generator as essential components.
- a radiation sensitive polymer composition generates an acid from an acid generator upon irradiation (exposure), and an acid that has protected an acidic group (for example, a carboxyl group) of the polymer by the action of the generated acid.
- the dissociable group is dissociated to expose the acidic group.
- the alkali solubility of the exposed portion of the resist is increased, and the exposed portion is dissolved and removed by the alkali developer, so that a positive resist pattern can be formed.
- the polymer preferably contains a structural unit having an acid-dissociable group, and more preferably contains 30 to 60 mol% of the structural unit with respect to all the structural units of the polymer.
- polymer examples include a polymer having a structural unit represented by the following formula.
- Examples of the acid generator include triphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyl diphenylsulfonium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio Phenium nonafluoro-n-butanesulfonate, triphenylsulfonium 2- (bicyclo [2.2.1] hepta-2'-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4- n-butoxynaphthyl) tetrahydrothiophenium 2- (bicyclo [2.2.1] hepta-2'-yl) -1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (bicyclo [2 2.1] hepta-2'-yl)
- the photoresist film is prepared by adding a solvent to the polymer component and preparing a coating solution by filtering with a filter having a pore diameter of about 30 nm as a solution having a total solid content concentration adjusted to 0.2% by mass to 20% by mass.
- the coating liquid can be formed by coating on a substrate using a conventionally known coating method such as spin coating, cast coating, roll coating or the like. In forming the photoresist film, pre-baking may be performed to volatilize the solvent.
- Step (2) This step is a step of forming the liquid immersion upper layer film by applying the liquid immersion upper layer film forming composition on the photoresist film.
- the immersion upper layer film By forming the immersion upper layer film, it is possible to prevent the immersion liquid from coming into direct contact with the photoresist film during the immersion exposure. It is possible to effectively prevent the lens of the projection exposure apparatus from being contaminated by components eluted from the resist film.
- the thickness of the liquid immersion upper layer film is preferably as close as possible to an odd multiple of ⁇ / 4m ( ⁇ : wavelength of radiation, m: refractive index of the protective film). This is because the reflection suppressing effect at the upper interface of the photoresist film is increased.
- Step (3) In this step, an immersion medium is disposed between the immersion upper layer film and the lens, and the photoresist film and the upper layer film are exposed through the immersion medium and a mask having a predetermined pattern. is there.
- the immersion medium a liquid having a refractive index higher than that of air is usually used, water is preferable, and pure water is more preferable. Note that the pH of the immersion liquid may be adjusted as necessary.
- a state where the immersion medium is interposed that is, a state where the immersion medium is filled between the lens of the exposure apparatus and the photoresist film
- radiation is irradiated through a mask having a predetermined pattern, and the photoresist film is removed. Let it be exposed.
- the radiation that can be used for the immersion exposure can be appropriately selected according to the type of the photoresist film or the immersion upper layer film to be used.
- visible rays For example, visible rays; ultraviolet rays such as g rays and i rays; excimer lasers, etc. Far ultraviolet rays; X-rays such as synchrotron radiation; various types of radiation such as charged particle beams such as electron beams can be used.
- an ArF excimer laser wavelength 193 nm
- a KrF excimer laser wavelength 248 nm
- the exposure conditions such as the radiation dose can be appropriately set according to the composition of the photoresist composition, the type of additive, and the like.
- baking is preferably performed after exposure.
- the baking temperature is appropriately adjusted depending on the type of the photoresist composition used, but is usually 30 ° C. to 200 ° C., preferably 50 ° C. to 150 ° C.
- Step (4) This step is a step of developing the exposed photoresist film and the upper layer film.
- an alkaline aqueous solution is preferable.
- the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, Triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3. 0] -5-nonane and the like.
- aqueous solutions of tetraalkylammonium hydroxides are preferred.
- a water-soluble organic solvent such as methanol or ethanol or a surfactant
- it wash cleans with water after image development normally. If it is appropriately dried after washing with water, the desired photoresist pattern can be formed.
- M-1 Methacrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-butyl) ester
- M-2 Vinylsulfonic acid
- M-3 Methacrylic acid (2,2,2 -Trifluoroethyl) ester
- M-4 Methacrylic acid (1-trifluoromethyl-2,2,2-trifluoroethyl) ester
- M-5 Dicyclopentyl methacrylate
- M-6 Methacrylic acid (1,1,1 -Trifluoro-2-trifluoromethyl-2-hydroxy-3-propyl) ester
- M-7 Methacrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-pentyl) ester
- M-8 2-methacryloyloxyethyl hexahydrophthalate
- This lower layer solution was diluted with isopropanol to 100 g, and transferred again to a separatory funnel. Thereafter, 50 g of methanol and 600 g of n-hexane were put into the above separatory funnel, separation and purification were performed, and the lower layer liquid was recovered after separation.
- the recovered lower layer solution was replaced with 4-methyl-2-pentanol to prepare a total amount of 250 g. After the preparation, 250 g of water was added for separation and purification. After separation, the upper layer liquid was recovered. The recovered upper layer liquid was replaced with 4-methyl-2-pentanol to obtain a resin solution.
- the solid content concentration is calculated from the mass of the residue after placing 0.3 g of the resin solution on an aluminum dish and heating on a hot plate heated to 140 ° C. for 1 hour, and then a liquid composition for forming an upper liquid immersion film was used for the preparation and yield calculation.
- the copolymer (P-1) contained in the obtained resin solution had Mw of 10,010, Mw / Mn of 1.55, and the yield was 75%.
- the content rate of structural unit (I) and structural unit (II) was 98: 2 (mol%).
- composition for forming liquid immersion upper layer film 92 parts by mass of polymer (P-1), 3 parts by mass of polymer (P-8), 5 parts by mass of polymer (P-22), and 4-methyl-2-pentanol as a [S] solvent, 634 parts by mass and 1,409 parts by mass of diisoamyl ether were mixed and stirred for 2 hours, and then filtered with a filter having a pore size of 200 nm to obtain a liquid immersion upper layer film-forming composition having a solid content concentration of 1.4% by mass. Prepared.
- Examples 2 to 108 and Comparative Examples 1 to 21 Each liquid immersion upper layer film-forming composition was prepared in the same manner as in Example 1 except that the types and blending amounts of the respective polymers were as described in Tables 2 to 4. In Tables 2 to 4, “-” means that the corresponding component was not used.
- the polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the polymerization solution was cooled with water to 30 ° C. or less, poured into 2,000 g of methanol, and the precipitated white powder was separated by filtration. The filtered white powder was washed twice with 400 g of methanol as a slurry, then filtered and dried at 50 ° C. for 17 hours to obtain a white powder polymer (D-1) (yield 74 g, Yield 74%).
- the polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the polymerization solution was cooled with water to 30 ° C. or less, poured into 2,000 g of methanol, and the precipitated white powder was separated by filtration. The filtered white powder was washed twice with 400 g of methanol in a slurry form, filtered, and dried at 50 ° C. for 17 hours to obtain a white powder polymer (D-2) (yield 73 g). , Yield 73%).
- the prepared photoresist composition was spin-coated on an 8-inch silicon wafer, and pre-baked on a hot plate at 90 ° C. for 60 seconds to form a 120 nm-thick photoresist film. Thereafter, using the DSA-10, the advancing contact angle (°) was promptly measured in an environment of room temperature 23 ° C., humidity 45%, and normal pressure. The wafer stage position of the DSA-10 is adjusted, and the wafer is set on the adjusted stage. Next, water is injected into the needle, and the position of the needle is finely adjusted to an initial position where water droplets can be formed on the wafer.
- the prepared photoresist composition was spin-coated on an 8-inch silicon wafer that had been previously subjected to hexamethyldisilazane (HMDS) treatment (100 ° C., 60 seconds) using the CLEAN TRACK ACT8. Pre-baking was performed at 90 ° C. for 60 seconds on a hot plate to form a 120 nm-thick photoresist film. Each liquid immersion upper layer film-forming composition was spin-coated on the formed photoresist film, and pre-baked at 90 ° C. for 60 seconds to form a liquid immersion upper layer film having a thickness of 30 nm.
- HMDS hexamethyldisilazane
- Ultra pure water was discharged from the rinse nozzle of CLEAN TRACK ACT8 onto the wafer for 60 seconds, and spin-drying was performed at 4,000 rpm for 15 seconds. Subsequently, using CLEAN TRACK ACT8, paddle development (developer: 2.38% TMAH aqueous solution) was performed for 60 seconds with an LD nozzle to remove the liquid immersion upper layer film. Although the upper layer film is removed by the above development, the photoresist film remains as it is because it is not exposed.
- the film thickness of the photoresist film is measured using Lambda Ace VM90 (manufactured by Dainippon Screen), and when the rate of change in film thickness is within 5%, between the photoresist film and the upper layer film It was judged that there was no intermixing. As a result, the immersion upper layer films formed from the compositions for forming an immersion upper layer film of Examples 1 to 108 were satisfactory without intermixing.
- an 8-inch silicon wafer 3 was prepared in which the HMDS processing layer 4 was performed using the CLEAN TRACK ACT 8 in advance at a processing condition of 100 ° C. for 60 seconds.
- a silicon rubber sheet 5 made of Kureha elastomer, a square having a thickness of 1.0 mm and a shape having a side of 30 cm
- a central portion cut into a circular shape having a diameter of 11.3 cm is placed. It was.
- the central portion (the cut-out portion 6) where the silicon rubber sheet 5 was cut out was positioned at the center of the wafer 3.
- the hollow portion 6 of the silicon rubber sheet 5 was filled with 10 mL of ultrapure water 7 using a 10 mL hole pipette.
- an 8-inch silicon wafer 10 different from the wafer 3 on which the lower layer antireflection film 8, the photoresist coating film 11 and the liquid immersion upper layer film 9 are formed in advance is prepared. It placed so that it might be located on the silicon rubber sheet 5 side, that is, while the liquid immersion upper layer film 9 and the ultrapure water 7 were in contact with each other, the ultrapure water 7 did not leak.
- the lower antireflection film 8, the photoresist film 11 and the liquid immersion upper film 9 on the wafer 10 were formed as follows.
- a composition for forming a lower antireflection film (ARC29A, manufactured by Brewer Science) was applied using the CLEAN TRACK ACT8 to a film thickness of 77 nm.
- the prepared photoresist composition was spin-coated on the lower antireflection film 8 using CLEAN TRACK ACT8, and baked at 115 ° C. for 60 seconds to form a photoresist film 11 having a thickness of 205 nm.
- each liquid immersion upper film forming composition was applied onto the photoresist film 11 to form a liquid immersion upper film 9. After placing the liquid immersion upper layer film 9 so as to be positioned on the silicon rubber sheet 5 side, the state was maintained for 10 seconds.
- the wafer 10 was removed, and the ultrapure water 7 that had been in contact with the liquid immersion upper layer film 9 was collected with a glass syringe.
- This ultrapure water 7 was used as a sample for analysis. Note that the recovery rate of the ultrapure water 7 filled in the cut-out portion 6 of the silicon rubber sheet 5 was 95% or more.
- the peak intensity of the anion part of the photoacid generator in the obtained analytical sample was measured by LC-MS (liquid chromatograph mass spectrometer) (LC part: SERIES1100, MS part made by AGILENT). : Mariner manufactured by Perseptive Biosystems, Inc.) under the following measurement conditions.
- each of the peak intensities of the 1 ppb, 10 ppb, and 100 ppb aqueous solutions was measured under the same conditions as those for the analytical sample to prepare a calibration curve.
- the elution amount (of the anion portion) of the acid generator relative to water was calculated.
- a calibration curve was prepared by measuring the peak intensities of 1 ppb, 10 ppb, and 100 ppb aqueous solutions under the same conditions as those for the analytical sample for the acid diffusion controller. Using this calibration curve, the elution amount of the acid diffusion controlling agent with respect to water was calculated.
- the evaluation of the elution amount is good when the sum of the elution amount of the anion portion of the acid generator calculated above and the elution amount of the acid diffusion controller is 5.0 ⁇ 10 ⁇ 12 mol / cm 2 or less. It was judged. As a result, the immersion upper layer films formed from the compositions for forming an immersion upper layer film of Examples 1 to 108 had a good elution amount.
- the measurement conditions are as follows. Column used: CAPCELL PAK MG, manufactured by Shiseido, 1 Flow rate: 0.2 mL / min, Elution solvent: Water / methanol (3/7) with 0.1% by weight of formic acid added Measurement temperature: 35 ° C.
- the lower antireflection film composition (ARC29A, manufactured by Brewer Science) is spin-coated, prebaked at 205 ° C. for 60 seconds, and a lower layer with a film thickness of 77 nm An antireflection film was formed.
- the prepared photoresist composition was spin-coated on the formed lower antireflection film, and prebaked at 90 ° C. for 60 seconds to form a 120 nm-thick photoresist film.
- Each liquid immersion upper layer film-forming composition was spin-coated on the formed photoresist film, and pre-baked at 90 ° C.
- the exposure amount for forming a line-and-space pattern (1L1S) having a line width of 90 nm in a one-to-one line width was determined as the optimum exposure amount.
- a scanning electron microscope S-9380, manufactured by Hitachi Keiki Co., Ltd.
- S-4200 manufactured by Hitachi Keiki Co., Ltd.
- the line width Lb in the middle of the photoresist pattern 2 formed on the substrate 1 and the line width La in the upper part of the photoresist pattern are measured, and 0.9 ⁇ La / Lb ⁇ 1.1.
- the patterning property was judged to be good.
- the liquid immersion upper layer films formed from the liquid immersion upper layer film forming compositions of Examples 1 to 108 had good patternability.
- a 12-inch silicon wafer having a 77 nm-thick lower layer antireflection film (ARC29A, manufactured by Brewer Science) on the surface was used as a substrate.
- CLEAN TRACK ACT12 product made from Tokyo Electron
- the photoresist composition prepared on the substrate was spin-coated with the CLEAN TRACK ACT12 and then pre-baked at 90 ° C. for 60 seconds to form a photoresist film having a thickness of 120 nm. Thereafter, each liquid immersion upper layer film-forming composition was spin-coated on the photoresist film and then pre-baked at 90 ° C.
- the liquid immersion upper layer film forming compositions of Examples 1 to 108 can form a liquid immersion upper layer film that can suppress the occurrence of watermark defects and bridge defects. all right.
- the bridging defects were not sufficiently satisfactory for the compositions for forming immersion upper layer films of Comparative Examples 1 to 7 and 15 to 21 using the polymer not containing the structural unit (I).
- the watermark defect was not sufficiently satisfactory in the compositions for forming a liquid immersion upper layer film of Comparative Examples 8 to 14 in the compositions for forming a liquid immersion upper layer film of Comparative Examples 8 to 14, the watermark defect was not sufficiently satisfactory.
- the present invention has a liquid immersion upper layer that has moderate water repellency and high solubility in a developer, and can suppress the occurrence of various defects such as watermark defects and bridge defects even when the scanning speed is high.
- a composition for forming a liquid immersion upper film capable of forming a film can be provided. Therefore, the composition for forming a liquid immersion upper layer film can be very suitably used in a semiconductor device manufacturing process that is expected to be further miniaturized in the future.
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Abstract
Description
R=k1・λ/NA
δ=k2・λ/NA2
λは、露光波長、NAは投影光学系の開口数、k1及びk2は、それぞれプロセス係数である。
R=k1・(λ/n)/NA
δ=k2・nλ/NA2
[A]下記式(1)で表される構造単位(I)を有する重合体(以下、「[A]重合体」とも称する)、及び
[S]溶媒
を含有する液浸上層膜形成用組成物である。
をさらに含有することが好ましい。
(1)基板上にフォトレジスト組成物を塗布してフォトレジスト膜を形成する工程、
(2)上記フォトレジスト膜上に当該液浸上層膜形成用組成物を塗布して液浸上層膜を形成する工程、
(3)上記液浸上層膜とレンズとの間に液浸媒体を配置し、この液浸媒体と所定のパターンを有するマスクとを介して上記フォトレジスト膜及び上記上層膜を露光する工程、並びに
(4)上記露光されたフォトレジスト膜及び上層膜を現像する工程
を有する。
本発明の液浸上層膜形成用組成物は、フォトレジスト組成物によって形成されるフォトレジスト膜の表面上に液浸上層膜を形成するために用いられるものであって、[A]重合体及び[S]溶媒を含有する。また、当該液浸上層膜形成用組成物は好適成分として、[B]重合体を含有してもよい。さらに、当該液浸上層膜形成用組成物は本発明の効果を損なわない限りにおいて、その他の重合体及びその他の任意成分を含有してもよい。以下、各成分を詳述する。
[A]重合体は、上記式(1)で表される構造単位(I)を有する。当該液浸上層膜形成用組成物が、構造単位(I)を有する[A]重合体を含有することで、形成される液浸上層膜は適度な撥水性を有しつつ、現像液に対する溶解性も併せ持つため、液浸露光時にフォトレジスト膜を保護し、水等の媒体に溶出することなく安定な塗膜を維持し、ウォーターマーク欠陥、バブル欠陥、パターン不良欠陥、ブリッジ欠陥等の欠陥の発生を効果的に抑制し、高解像度のレジストパターンを形成可能である。また、[A]重合体は、構造単位(II)、構造単位(III)、構造単位(IV)をさらに有することが好ましい。なお、[A]重合体は、各構造単位を2種以上有していてもよい。以下、各構造単位を詳述する。
構造単位(I)は、上記式(1)で表される。上記式(1)中、R1は、水素原子、メチル基又はトリフルオロメチル基である。構造単位(I)を与える単量体としては、(メタ)アクリル酸(1,1,1-トリフルオロ-2-トリフルオロメチル-2-ヒドロキシ-4-ブチル)エステルが好ましい。
構造単位(II)は、スルホ基を有する構造単位である。構造単位(II)としては、例えば下記式(2-1)、式(2-2)で表される構造単位等が挙げられる。
構造単位(III)は、上記式(3)で表される。上記式(3)中、R2は、水素原子、メチル基又はトリフルオロメチル基である。R3は、直鎖状若しくは分岐状の炭素数1~12の1価の炭化水素基、又は炭素数3~20の1価の脂環式基である。但し、上記炭化水素基及び脂環式基が有する水素原子の少なくとも1つは、フッ素原子で置換されている。
メチル基、エチル基、1,3-プロピル基、1,2-プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、1-メチル-1,3-プロピル基、2-メチル1,3-プロピル基、2-メチル-1,2-プロピル基、1-メチル-1,4-ブチル基、2-メチル-1,4-ブチル基等の飽和鎖状炭化水素基;
1,3-シクロブチル基、1,3-シクロペンチル基、1,4-シクロヘキシル基、1,5-シクロオクチル基等の単環式炭化水素環基;
1,4-ノルボルニル基、2,5-ノルボルニル基、1,5-アダマンチル基、2,6-アダマンチル基等の多環式炭化水素環基
の部分フッ素化又はパーフルオロアルキル基が好ましい。
構造単位(IV)は、上記式(4)で表される。上記式(4)中、R4は、水素原子、メチル基又はトリフルオロメチル基である。R5は、直鎖状若しくは分岐状の炭素数1~12の1価の炭化水素基、又は炭素数3~20の1価の脂環式基である。
[A]重合体は、本発明の効果を損なわない範囲において、その他の構造単位としての構造単位(V)を有していてもよい。
当該液浸上層膜形成用組成物は、上述の構造単位(I)及び構造単位(V)からなる群より選択される少なくとも1種の構造単位、並びに構造単位(III)を有し、かつ[A]重合体よりもフッ素原子含有率が高い[B]重合体をさらに含有することが好ましい。[B]重合体は、[A]重合体よりもフッ素原子含有率が高いことから、[A]重合体よりも撥水性に優れる。そうすると、当該液浸上層膜形成用組成物が[B]重合体をさらに含有することで、[B]重合体は、[A]重合体に対し表層部に偏在化され、後退接触角が低下せず液滴残りに伴うウォーターマーク欠陥を防止できる。
当該液浸上層膜形成用組成物は、本発明の効果を損なわない範囲において上述の[A]重合体及び[B]重合体以外のその他の重合体を含有してもよい。その他の重合体の態様としては、
(i)構造単位(V)及び構造単位(II)を有する重合体;
(ii)後述する構造単位(VI)及び構造単位(II)を有する重合体
等が挙げられる。構造単位(II)及び構造単位(V)の詳細については[A]重合体の項にて説明した内容を適用することができる。
構造単位(VI)としては、例えば下記式(6-1)、式(6-2)、式(6-3)で表される構造単位等が挙げられる。
各重合体は、例えば重合開始剤や連鎖移動剤の存在下、重合溶媒中で、各構造単位を与える単量体をラジカル重合することによって合成できる。
装置:HLC-8120(東ソー製)
カラム:G2000HXL2本、G3000HXL1本、G4000HXL1本(以上、東ソー製)
溶出溶媒:テトラヒドロフラン
カラム温度:40℃
流速:1.0mL/分
標準物質:単分散ポリスチレン
本発明の液浸上層膜形成用組成物は、上記重合体成分を溶解することを目的として[S]溶媒を含有する。[S]溶媒としては、フォトレジスト膜上に塗布する際に、フォトレジスト膜とインターミキシングを発生する等のリソグラフィ性能を劣化させない溶媒が好ましい。
当該液浸上層膜形成用組成物は、上記成分に加え、所期の効果を損なわない範囲で必要に応じて塗布性、消泡性、レベリング性等を向上させる目的で界面活性剤等のその他の任意成分を配合することもできる。
当該液浸上層膜形成用組成物は、[S]溶媒に[A]重合体、必要に応じて[B]重合体、その他の重合体、その他の任意成分を混合することによって溶解又は分散させた状態に調製される。また、当該液浸上層膜形成用組成物は、全固形分濃度が所望の値となるように調製された溶液を、孔径200nm程度のフィルターでろ過することにより調製できる。なお、固形分濃度としては特に限定されないが通常0.1質量%~20.0質量%である。
(1)基板上にフォトレジスト組成物を塗布してフォトレジスト膜を形成する工程、
(2)上記フォトレジスト膜上に当該液浸上層膜形成用組成物を塗布して液浸上層膜を形成する工程、
(3)上記液浸上層膜とレンズとの間に液浸媒体を配置し、この液浸媒体と所定のパターンを有するマスクとを介して上記フォトレジスト膜及び上記上層膜を露光する工程、並びに
(4)上記露光されたフォトレジスト膜及び上層膜を現像する工程
を有する。
本工程は、基板上にフォトレジスト組成物を塗布してフォトレジスト膜を形成する工程である。基板としては、通常、シリコンウェハ、アルミニウムで被覆したシリコンウェハ等が用いられる。フォトレジスト膜の特性を最大限に引き出すため、予め基板の表面に有機系又は無機系の反射防止膜を形成しておくことも好ましい(例えば、特公平6-12452号公報等を参照)。
本工程は、上記フォトレジスト膜上に当該液浸上層膜形成用組成物を塗布して液浸上層膜を形成する工程である。液浸上層膜を形成することで、液浸露光の際に液浸液がフォトレジスト膜と直接接触することが防止され、液浸液の浸透によってフォトレジスト膜のリソグラフィ性能が低下したり、フォトレジスト膜から溶出する成分により投影露光装置のレンズが汚染されたりする事態を効果的に防止することが可能となる。
本工程は、上記液浸上層膜とレンズとの間に液浸媒体を配置し、この液浸媒体と所定のパターンを有するマスクとを介して上記フォトレジスト膜及び上記上層膜を露光する工程である。
本工程は、上記露光されたフォトレジスト膜及び上記上層膜を現像する工程である。現像工程に使用される現像液としては、アルカリ性の水溶液が好ましい。アルカリとしては、例えば水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、珪酸ナトリウム、メタ珪酸ナトリウム、アンモニア、エチルアミン、n-プロピルアミン、ジエチルアミン、ジ-n-プロピルアミン、トリエチルアミン、メチルジエチルアミン、ジメチルエタノールアミン、トリエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、ピロール、ピペリジン、コリン、1,8-ジアザビシクロ-[5.4.0]-7-ウンデセン、1,5-ジアザビシクロ-[4.3.0]-5-ノナン等が挙げられる。これらのうち、テトラアルキルアンモニウムヒドロキシド類の水溶液が好ましい。
各重合体の合成に用いた単量体を下記に示す。
M-2:ビニルスルホン酸
M-3:メタクリル酸(2,2,2-トリフルオロエチル)エステル
M-4:メタクリル酸(1-トリフルオロメチル-2,2,2-トリフルオロエチル)エステル
M-5:メタクリル酸ジシクロペンチル
M-6:メタクリル酸(1,1,1-トリフルオロ-2-トリフルオロメチル-2-ヒドロキシ-3-プロピル)エステル
M-7:メタクリル酸(1,1,1-トリフルオロ-2-トリフルオロメチル-2-ヒドロキシ-4-ペンチル)エステル
M-8:ヘキサヒドロフタル酸2-メタクリロイルオキシエチル
[合成例1]
構造単位(I)を与える単量体(M-1)46.81g(85モル%)、及び重合開始剤として2,2’-アゾビス-(2-メチルプロピオン酸メチル)4.53gをイソプロパノール40.00gに溶解させ単量体溶液を調製した。一方、温度計及び滴下漏斗を備えた200mLの三つ口フラスコにイソプロパノール50gを投入し、30分間窒素パージした。窒素パージの後、フラスコ内をマグネティックスターラーで攪拌しながら、80℃になるように加熱した。滴下漏斗を用い、調製した単量体溶液を2時間かけて滴下した。滴下終了後、更に1時間反応を行い、構造単位(II)を与える単量体(M-2)3.19g(15モル%)のイソプロパノール溶液10gを30分かけて滴下した。その後、更に1時間反応を行った後、30℃以下に冷却して、共重合液を得た。得られた共重合液を150gに濃縮した後、分液漏斗に移した。この分液漏斗にメタノール50gとn-ヘキサン600gを投入し、分離精製を実施した。分離後、下層液を回収した。この下層液をイソプロパノールで希釈して100gとし、再度分液漏斗に移した。その後、メタノール50gとn-ヘキサン600gを上記分液漏斗に投入して、分離精製を実施し、分離後、下層液を回収した。回収した下層液を4-メチル-2-ペンタノールに置換し、全量を250gに調製した。調製後、水250gを加えて分離精製を実施し、分離後、上層液を回収した。回収した上層液は、4-メチル-2-ペンタノールに置換して樹脂溶液とした。固形分濃度は、その樹脂溶液0.3gをアルミ皿にのせ、140℃に加熱したホットプレート上で1時間加熱した後の残渣の質量から算出し、その後の液浸上層膜形成用組成物溶液の調製と収率計算に利用した。得られた樹脂溶液に含有されている共重合体(P-1)の、Mwは10,010、Mw/Mnは1.55であり、収率は75%であった。構造単位(I)及び構造単位(II)の含有率は、98:2(モル%)であった。
使用した単量体の種類を表1に記載の通りとした以外は、合成例1と同様に操作して重合体をそれぞれ合成した。なお、表1中の「-」は該当する単量体を使用しなかったことを意味する。また、表1中の数値は、各単量体が与える構造単位の含有率(%)である。
[合成例16]
構造単位(V)を与える単量体として(M-7)37.3gをメチルエチルケトン4.5gに予め溶解させた単量体溶液を調製した。一方、温度計及び滴下漏斗を備えた500mLの三口フラスコに上述の構造単位(III)を与える単量体(M-4)69.6gと2,2-アゾビス(2-メチルイソプロピオン酸メチル)4.5gとメチルエチルケトン95.5gを投入し、30分間窒素パージした。窒素パージ後、フラスコ内をマグネティックスターラーで撹拌しながら75℃になるように加熱した。滴下漏斗を使用し、予め準備しておいた単量体溶液を5分かけて滴下し6時間熟成させた後、30℃以下になるまで冷却することにより共重合溶液を得た。得られた共重合溶液を150gに濃縮し分液漏斗に移し、メタノール150g及びn-ヘキサン750gを分液漏斗に投入して分離精製を行い、下層液を回収した。回収した下層液の溶媒を、4-メチル-2-ペンタノールに置換した。共重合体(P-16)のMwは7,500、Mw/Mnは1.50であり、収率は50%であった。構造単位(V)及び構造単位(III)の含有率は、60:40(モル%)であった。
使用した単量体の種類を表1に記載の通りとした以外は、合成例16と同様に操作してその他の重合体をそれぞれ合成した。なお、表1中の「-」は、該当する単量体を使用しなかったことを意味する。また、表1中の数値は、各単量体が与える構造単位の含有率(%)である。
構造単位(VI)を与える単量体(M-8)46.95g(85モル%)、及び重合開始剤としての2,2’-アゾビス-(2-メチルプロピオン酸メチル)6.91gをイソプロパノール100gに溶解させた単量体溶液を調製した。一方、温度計及び滴下漏斗を備えた500mLの三つ口フラスコにイソプロパノール50gを投入し、30分間窒素パージした。窒素パージの後、フラスコ内をマグネティックスターラーで攪拌しながら、80℃になるように加熱した。滴下漏斗を用い、調製した単量体溶液を2時間かけて滴下した。滴下終了後、更に1時間反応を行い、構造単位(II)を与える単量体(M-2)3.05g(15モル%)のイソプロパノール溶液10gを30分かけて滴下した。その後、更に1時間反応を行った後、30℃以下に冷却して、共重合溶液を得た。得られた共重合液を150gに濃縮した後、分液漏斗に移した。この分液漏斗にメタノール50gとn-ヘキサン600gを投入し、分離精製を実施した。分離後、下層液を回収した。この下層液をイソプロパノールで希釈して100gとし、再度、分液漏斗に移した。その後、メタノール50gとn-ヘキサン600gを上記分液漏斗に投入して、分離精製を実施し、分離後、下層液を回収した。回収した下層液を4-メチル-2-ペンタノールに置換し、全量を250gに調整した。調整後、水250gを加えて分離精製を実施し、分離後、上層液を回収した。回収した上層液は、4-メチル-2-ペンタノールに置換して樹脂溶液とした。得られた樹脂溶液に含有されている共重合体(P-22)の、Mwは11,060、Mw/Mnは1.55であり、収率は75%であった。構造単位(VI)及び構造単位(II)の含有率は、96:4(モル%)であった。
[実施例1]
重合体(P-1)92質量部、重合体(P-8)3質量部、重合体(P-22)5質量部、及び[S]溶媒としての4-メチル-2-ペンタノール5,634質量部及びジイソアミルエーテル1,409質量部を混合し、2時間撹拌した後、孔径200nmのフィルターでろ過することにより、固形分濃度1.4質量%の液浸上層膜形成用組成物を調製した。
各重合体の種類及び配合量を表2~表4に記載の通りとした以外は、実施例1と同様に操作して各液浸上層膜形成用組成物を調製した。なお、表2~表4中の「-」は、該当する成分を使用しなかったことを意味する。
フォトレジスト組成物用重合体の合成に用いた単量体の構造は下記式で表される。
上記化合物(M-9)53.93g(50モル%)、化合物(M-10)35.38g(40モル%)、化合物(M-11)10.69g(10モル%)を2-ブタノン200gに溶解し、更にジメチル2,2’-アゾビス(2-メチルプロピオネート)5.58gを投入した単量体溶液を調製し、100gの2-ブタノンを投入した500mLの三口フラスコを30分窒素パージした。窒素パージの後、反応釜を攪拌しながら80℃に加熱し、調製した単量体溶液を滴下漏斗を用いて3時間かけて滴下した。滴下開始を重合開始時間とし、重合反応を6時間実施した。重合終了後、重合溶液は水冷することにより30℃以下に冷却し、2,000gのメタノールへ投入し、析出した白色粉末をろ別した。ろ別した白色粉末を400gのメタノールにてスラリー状で2回洗浄した後、ろ別し、50℃にて17時間乾燥し、白色粉末の重合体(D-1)を得た(収量74g、収率74%)。重合体(D-1)はMwが6,900、Mw/Mn=1.70、13C-NMR分析の結果、化合物(M-9)、化合物(M-10)、化合物(M-11)に由来する各構造単位の含有率は、53.0:37.2:9.8(モル%)であった。なお、各単量体由来の低分子量成分の含有量は、重合体(D-1)100質量%に対して、0.03質量%であった。
上記化合物(M-9)47.54g(46モル%)、化合物(M-10)12.53g(15モル%)、化合物(M-12)39.93g(39モル%)を2-ブタノン200gに溶解し、更に2,2’-アゾビス(イソブチロニトリル)4.08gを投入した単量体溶液を調製した。一方、100gの2-ブタノンを投入した1,000mLの三口フラスコを用意し、30分窒素パージした。窒素パージの後、三口フラスコ内の内容物を攪拌しながら80℃に加熱し、調製した単量体溶液を滴下漏斗を用いて3時間かけて滴下した。滴下開始を重合開始時間とし、重合反応を6時間実施した。重合終了後、重合溶液は水冷することにより30℃以下に冷却し、2,000gのメタノールへ投入し、析出した白色粉末をろ別した。ろ別された白色粉末を400gのメタノールにてスラリー状で2回洗浄した後、ろ別し、50℃にて17時間乾燥し、白色粉末の重合体(D-2)を得た(収量73g、収率73%)。重合体(D-2)はMwが5,700、Mw/Mn=1.7、13C-NMR分析の結果、化合物(M-9)、化合物(M-10)、化合物(M-12)に由来する各構造単位の含有率は51.4:14.6:34.0(モル%)であった。
[合成例26]
上記重合体(D-1)30質量部及び(D-2)70質量部、酸発生剤としてのトリフェニルスルホニウムノナフルオロ-n-ブタンスルホネート4質量部及び1-(4-n-ブトキシナフタレン-1-イル)テトラヒドロチオフェニウムノナフルオロ-n-ブタンスルホネート5質量部、酸拡散制御剤としてのR-(+)-(tert-ブトキシカルボニル)-2-ピペリジンメタノール0.83質量部、並びに溶媒として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1,710質量部及びシクロヘキサノン730質量部を混合し、フォトレジス組成物を調製した。
調製した各液浸上層膜形成用組成物及びフォトレジスト組成物を用いて、下記の評価を実施した。
8インチシリコンウェハ上に、CLEAN TRACK ACT8(東京エレクトロン製)を使用して、各液浸上層膜形成用組成物をスピンコートし、90℃で60秒ベークを行い、膜厚90nmの液浸上層膜を形成した。なお、膜厚はラムダエースVM90(大日本スクリーン製)を使用して測定した。CLEAN TRACK ACT8を使用して60秒間パドル現像(現像液は2.38%TMAH水溶液を使用)を行い、振り切りによりスピンドライした後、ウェハ表面を観察した。その結果、実施例1~108の液浸上層膜形成用組成物から形成された液浸上層膜は、ウェハ表面に残渣がなく現像されており、除去性が良好であった。
8インチシリコンウェハ上に、各液浸上層膜形成用組成物をスピンコートし、ホットプレート上で90℃で60秒プレベークを行い、膜厚30nmの液浸上層膜を形成した。その後、DSA-10(KRUS製)を使用して、速やかに室温23℃、湿度45%、常圧の環境下、後退接触角(°)を測定した。DSA-10のウェハステージ位置を調整し、この調整したステージ上に上記ウェハをセットする。次に、針に水を注入し、ウェハ上に水滴を形成可能な初期位置に針の位置を微調整する。その後、この針から水を排出させてウェハ上に25μLの水滴を形成し、一旦この水滴から針を引き抜き、再び初期位置に針を引き下げて水滴内に配置する。続いて、10μL/minの速度で90秒間、針によって水滴を吸引すると同時に接触角を毎秒1回、合計で90回測定する。接触角の測定値が安定した時点から20秒間の接触角についての平均値を算出して後退接触角(°)とした。その結果、実施例1~108の液浸上層膜形成用組成物から形成された液浸上層膜の後退接触角は65.0°以上であり良好であった。
8インチシリコンウェハ上に、調製したフォトレジスト組成物をスピンコートし、ホットプレート上で90℃で60秒プレベークを行い、膜厚120nmのフォトレジスト膜を形成した。その後、上記DSA-10を使用して、速やかに室温23℃、湿度45%、常圧の環境下、前進接触角(°)を測定した。DSA-10のウェハステージ位置を調整し、この調整したステージ上に上記ウェハをセットする。次に、針に水を注入し、ウェハ上に水滴を形成可能な初期位置に針の位置を微調整する。その後、この針から水を排出させてウェハ上に15μLの水滴を形成し、一旦この水滴から針を引き抜き、再び初期位置に針を引き下げて水滴内に配置する。続いて、10μL/minの速度で90秒間、針によって水滴を吐出すると同時に接触角を毎秒1回、合計で90回測定する。接触角の測定値が安定した時点から20秒間の接触角についての平均値を算出して前進接触角(°)とした。その結果、実施例1~108の液浸上層膜形成用組成物から形成された液浸上層膜の前進接触角は95.0°以下であり良好であった。
上記CLEAN TRACK ACT8を使用して予めヘキサメチルジシラザン(HMDS)処理(100℃、60秒)を行った8インチシリコンウェハ上に、調製したフォトレジスト組成物ををスピンコートした。ホットプレート上で90℃で60秒プレベークを行い、膜厚120nmのフォトレジスト膜を形成した。形成したフォトレジスト膜上に、各液浸上層膜形成用組成物をスピンコートし、90℃で60秒プレベークを行い膜厚30nmの液浸上層膜を形成した。CLEAN TRACK ACT8のリンスノズルから、ウェハ上に超純水を60秒間吐出させ、4,000rpmで15秒間振り切りのスピンドライを行った。次いで、CLEAN TRACK ACT8を使用し、LDノズルにてパドル現像(現像液:2.38%TMAH水溶液)を60秒間行って、液浸上層膜を除去した。なお、上記の現像によって上層膜は除去されるが、フォトレジスト膜は未露光であるためにそのまま残存する。現像の前後に、ラムダエースVM90(大日本スクリーン製)を使用してフォトレジスト膜の膜厚測定を行い、膜厚の変化率が5%以内である場合は、フォトレジスト膜と上層膜間でのインターミキシングがないと判断した。その結果、実施例1~108の液浸上層膜形成用組成物から形成された液浸上層膜は、インターミキシングがなく良好であった。
図2及び図3に示すように、予め上記CLEAN TRACK ACT8を用いて、処理条件100℃、60秒でHMDS処理層4を行った8インチシリコンウェハ3を用意した。このウェハ3のHMDS処理層4側の面に、中央部が直径11.3cmの円形状にくり抜かれたシリコンゴムシート5(クレハエラストマー製、厚み1.0mm、形状1辺30cmの正方形)を載せた。このとき、ウェハ3の中心部にシリコンゴムシート5のくり抜かれた中央部(くり抜き部6)が位置するようにした。次いで、シリコンゴムシート5のくり抜き部6に、10mLホールピペットを用いて10mLの超純水7を満たした。一方、予め下層反射防止膜8、フォトレジスト塗膜11及び液浸上層膜9が形成されたウェハ3とは別の8インチシリコンウェハ10を用意し、このウェハ10を、液浸上層膜9が上記シリコンゴムシート5側に位置するように、即ち液浸上層膜9と超純水7とを接触しつつ、超純水7が漏れないように載せた。なお、上記ウェハ10上の下層反射防止膜8、フォトレジスト膜11及び液浸上層膜9は、次のように形成した。下層反射防止膜形成用組成物(ARC29A、ブルワー・サイエンス製)を上記CLEAN TRACK ACT8を用いて膜厚77nmとなるように塗布した。次いで、調製したフォトレジスト組成物を、CLEAN TRACK ACT8を用いて下層反射防止膜8上にスピンコートし、115℃で60秒間ベークすることにより膜厚205nmのフォトレジスト膜11を形成した。その後、フォトレジスト膜11上に、各液浸上層膜形成用組成物を塗布して液浸上層膜9を形成した。液浸上層膜9がシリコンゴムシート5側に位置するように載せた後、その状態のまま10秒間保った。その後、ウェハ10を取り除き、液浸上層膜9と接触していた超純水7をガラス注射器にて回収した。この超純水7を分析用サンプルとした。なお、シリコンゴムシート5のくり抜き部6に満たした超純水7の回収率は95%以上であった。続いて、得られた分析用サンプル(超純水)中の光酸発生剤のアニオン部のピーク強度を、LC-MS(液体クロマトグラフ質量分析計)(LC部:AGILENT製のSERIES1100、MS部:Perseptive Biosystems,Inc.製のMariner)を用いて下記の測定条件により測定した。その際、フォトレジスト組成物に用いた酸発生剤について、1ppb、10ppb及び100ppb水溶液の各ピーク強度を、分析用サンプルの測定条件と同様の条件で測定して検量線を作成した。この検量線を用いて、水に対する酸発生剤の(アニオン部の)溶出量を算出した。また、同様にして酸拡散制御剤について1ppb、10ppb及び100ppb水溶液の各ピーク強度を分析用サンプルの測定条件と同様の条件で測定して検量線を作成した。この検量線を用いて、水に対する酸拡散制御剤の溶出量を算出した。溶出量の評価は、上記算出された酸発生剤のアニオン部の溶出量と酸拡散制御剤の溶出量の和が、5.0×10-12mol/cm2以下であった場合を良好と判断した。その結果、実施例1~108の液浸上層膜形成用組成物から形成された液浸上層膜は、溶出量が良好であった。測定条件は以下のとおりである。
使用カラム:CAPCELL PAK MG、資生堂製、1本、
流量:0.2mL/分、
流出溶媒:水/メタノール(3/7)に0.1質量%のギ酸を添加したもの
測定温度:35℃
上記CLEAN TRACK ACT8を用いて、処理条件100℃、60秒でHMDS処理を行った8インチシリコンウェハを用意した。この8インチシリコンウェハ上に、調製したフォトレジスト組成物をスピンコートし、ホットプレート上で90℃で60秒間プレベークし、膜厚120nmのフォトレジスト膜を形成した。このフォトレジスト膜上に、各液浸上層膜形成用組成物をスピンコートし、90℃で60秒間プレベークし、膜厚30nmの液浸上層膜を形成した。その後、パターンが形成されていない擦りガラスを介して露光を行った。次いで、液浸上層膜上にCLEAN TRACK ACT8のリンスノズルから超純水を60秒間吐出させ、4,000rpmで15秒間振り切りによりスピンドライを行った。次に、CLEAN TRACK ACT8のLDノズルによってパドル現像を60秒間行い、液浸上層膜を除去した。なお、このパドル現像では現像液として2.38%TMAH水溶液を使用した。現像後、液浸上層膜の溶け残りの程度を、KLA2351(KLAテンコール製)で測定し、ブロッブ欠陥を評価した。検出された現像剥離欠陥が200個以下の場合を良好と判断した。その結果、実施例1~108の液浸上層膜形成用組成物から形成された液浸上層膜は、ブロッブ欠陥が200個以下であり良好であった。
8インチシリコンウェハ上に、上記CLEAN TRACK ACT8を使用して、下層反射防止膜用組成物(ARC29A、ブルワー・サイエンス製)をスピンコートし、205℃で60秒プレベークを行い、膜厚77nmの下層反射防止膜を形成した。形成した下層反射防止膜上に、調製したフォトレジスト組成物をスピンコートし、90℃で60秒プレベークを行い膜厚120nmのフォトレジスト膜を形成した。形成したフォトレジスト膜上に、各液浸上層膜形成用組成物をスピンコートし、90℃で60秒プレベークを行い膜厚30nmの液浸上層膜を形成した。次いで、ArF投影露光装置(S306C、ニコン製)を使用し、NA:0.78、シグマ:0.85、2/3Annの光学条件にて露光を行い、CLEAN TRACK ACT8のリンスノズルから、ウェハ上に超純水を60秒間吐出させ、4,000rpmで15秒間振り切りのスピンドライを行った。その後、CLEAN TRACK ACT8のホットプレートを使用して115℃で60秒ポストエクスポージャーベークを行い、LDノズルにてパドル現像(現像液:2.38%TMAH水溶液)を30秒間行った。超純水にてリンスした後、4,000rpmで15秒間振り切ることによってスピンドライした。形成されたフォトレジストパターンについて、線幅90nmのライン・アンド・スペースパターン(1L1S)を1対1の線幅に形成する露光量を最適露光量とした。なお、測定には走査型電子顕微鏡(S-9380、日立計測器製)を使用した。また、線幅90nmライン・アンド・スペースパターンの断面形状を、走査型電子顕微鏡(S-4200、日立計測器製)にて観察した。図1に示すように基板1上に形成されたフォトレジストパターン2の中間における線幅Lbと、フォトレジストパターン上部における線幅Laを測定し、0.9≦La/Lb≦1.1であった場合をパターンニング性が良好と判断した。その結果、実施例1~108の液浸上層膜形成用組成物から形成された液浸上層膜は、パターニング性が良好であった。
表面に膜厚77nmの下層反射防止膜(ARC29A、ブルワー・サイエンス製)を形成した12インチシリコンウェハを基板とした。なお、この下層反射防止膜の形成には、CLEAN TRACK ACT12(東京エレクトロン製)を用いた。次いで、基板上に調製したフォトレジスト組成物を上記CLEAN TRACK ACT12にて、スピンコートした後、90℃で60秒間プレベークし膜厚120nmのフォトレジスト膜を形成した。その後、フォトレジスト膜上に各液浸上層膜形成用組成物をスピンコートした後、90℃で60秒間プレベークし、膜厚30nmの液浸上層膜を形成した。次に、ArF投影露光装置(S610C、ニコン製)にてNA=0.85、σ0/σ1=0.97/0.78、Azimuthの条件で、マスクパターンを介して露光を行った。この際、液浸上層膜上面と液浸露光機レンズとの間には液浸溶媒として純水を配置した。次いで、115℃で60秒間焼成した後、2.38質量%のテトラメチルアンモニウムヒドロキシド水溶液により、23℃で60秒間現像し、水洗し、乾燥し、ポジ型のフォトレジストパターンを形成した。その後、線幅100nmのライン・アンド・スペースパターン(1L1S)について、KLA2810(KLA-Tencor製)にて欠陥を測定し、また走査型電子顕微鏡(S-9380、日立ハイテクノロジーズ製)を用いて観察し、ArFエキシマレーザー液浸露光由来と予想されるウォーターマーク欠陥(water-mark欠陥)とバブル欠陥とを区別した。検出されたウォーターマーク欠陥が30個未満の場合は、「AA」、30個以上50個未満の場合は「A」(良好と判断)、50個以上100個未満の場合は「B」(やや良好と判断)、100個を超えた場合は「C」(不良と判断)とした。評価結果を表3に示す。なお、表3中、「ウォーターマーク欠陥」は本評価を示す。結果を表2~表4にあわせて示す。バブル欠陥は、検出されたバブル欠陥が50個以下の場合を良好と判断した。その結果、実施例1~108の液浸上層膜形成用組成物から形成された液浸上層膜は、バブル欠陥が50個以下であり良好であった。
上記「ウォーターマーク欠陥」の評価と同様に操作して、ポジ型のフォトレジストパターンを形成し、その後、線幅100nmのライン・アンド・スペースパターン(1L1S)について、KLA2810(KLA-Tencor製)にて欠陥を測定し、また走査型電子顕微鏡(S-9380、日立ハイテクノロジーズ製)を用いて観察し、ブリッジ欠陥を確認した。検出されたブリッジ欠陥が50個未満の場合は「A」(良好と判断)、50個以上100個未満の場合は「B」(やや良好と判断)、100個を超えた場合は「C」(不良と判断)とした。結果を表2~表4にあわせて示す。
2 フォトレジストパターン
3 8インチシリコンウェハ
4 ヘキサメチルジシラザン処理層
5 シリコンゴムシート
6 くり抜き部
7 超純水
8 下層反射防止膜
9 液浸上層膜
10 8インチシリコンウエハ
11 フォトレジスト膜
Claims (7)
- [A]重合体が、スルホ基を有する構造単位(II)をさらに有する請求項1に記載の液浸上層膜形成用組成物。
- [B]構造単位(I)及び構造単位(III)を有し、かつ[A]重合体よりもフッ素原子含有率が高い重合体
をさらに含有する請求項1に記載の液浸上層膜形成用組成物。 - [B]重合体が、構造単位(IV)をさらに有する請求項5に記載の液浸上層膜形成用組成物。
- (1)基板上にフォトレジスト組成物を塗布してフォトレジスト膜を形成する工程、
(2)上記フォトレジスト上膜に請求項1に記載の液浸上層膜形成用組成物を塗布して液浸上層膜を形成する工程、
(3)上記液浸上層膜とレンズとの間に液浸媒体を配置し、この液浸媒体と所定のパターンを有するマスクとを介して上記フォトレジスト膜及び上記上層膜を露光する工程、並びに
(4)上記露光されたフォトレジスト膜及び上層膜を現像する工程
を有するフォトレジストパターン形成方法。
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KR1020127030040A KR20130086139A (ko) | 2010-05-18 | 2011-05-18 | 액침 상층막 형성용 조성물 및 포토레지스트 패턴 형성 방법 |
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US20160109801A1 (en) | 2016-04-21 |
US9261789B2 (en) | 2016-02-16 |
US20170160637A9 (en) | 2017-06-08 |
TW201202857A (en) | 2012-01-16 |
US20120021359A1 (en) | 2012-01-26 |
JP5725020B2 (ja) | 2015-05-27 |
JPWO2011145663A1 (ja) | 2013-07-22 |
KR20130086139A (ko) | 2013-07-31 |
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