WO2006011427A1 - 含フッ素化合物、含フッ素ポリマー、レジスト組成物、およびレジスト保護膜組成物 - Google Patents
含フッ素化合物、含フッ素ポリマー、レジスト組成物、およびレジスト保護膜組成物 Download PDFInfo
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- WO2006011427A1 WO2006011427A1 PCT/JP2005/013507 JP2005013507W WO2006011427A1 WO 2006011427 A1 WO2006011427 A1 WO 2006011427A1 JP 2005013507 W JP2005013507 W JP 2005013507W WO 2006011427 A1 WO2006011427 A1 WO 2006011427A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/40—Halogenated unsaturated alcohols
- C07C33/42—Halogenated unsaturated alcohols acyclic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/30—Compounds having groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/40—Halogenated unsaturated alcohols
- C07C33/42—Halogenated unsaturated alcohols acyclic
- C07C33/423—Halogenated unsaturated alcohols acyclic containing only double bonds as unsaturation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/17—Unsaturated ethers 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
- C08F214/00—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 halogen
- C08F214/18—Monomers containing fluorine
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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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/20—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
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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
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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
- G03F7/0395—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 a backbone with alicyclic moieties
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
- Y10S430/115—Cationic or anionic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/146—Laser beam
Definitions
- Fluorine-containing compound Fluorine-containing compound, fluorine-containing polymer, resist composition, and resist protective film composition
- the present invention relates to a novel fluorine-containing compound, a fluorine-containing polymer, a method for producing the same, and a resist composition or a resist protective film composition containing the same.
- a fluorine-containing polymer having a functional group a functional group-containing fluorine-containing polymer used for a fluorine-based ion exchange membrane or a curable fluorine resin coating is known. All of these are linear polymers having a basic skeleton, and can be obtained by copolymerization of fluoroolefin represented by tetrafluoroethylene and a monomer having a functional group.
- Polymers containing a functional group and having a fluorinated alicyclic structure in the main chain are also known.
- a method for introducing a functional group into a polymer having a fluorinated aliphatic ring structure in the main chain a method using a terminal group of the polymer obtained by polymerization, a side chain of the polymer by treating the polymer at a high temperature, or
- a resist material that utilizes an acid-catalyzed reaction as a reaction mechanism is patterned through processes such as resist coating formation, exposure, beta after exposure, and development.
- the acid generated by irradiation with active actinic radiation is deactivated by a reaction with a compound that reacts with an acid such as an amine floating as an impurity in the atmosphere, thereby preventing the formation of a resist image.
- a change in sensitivity is caused. This is described in Non-Patent Document 1.
- exposure between exposure and beta after exposure has a significant adverse effect on resist properties. In other words, if the exposure time between exposure and beta after exposure becomes longer, the resist sensitivity decreases rapidly and the pattern cannot be formed.
- the PED effect post execution delay effect
- Patent Document 5 As one of the methods for reducing the PED effect, for example, a method described in Patent Document 5 for forming a polymer film (resist protective film) that is incompatible with a resist film on a resist film is known. It is. In this method, a resist protective film is formed in order to prevent amin or the like floating in the atmosphere from entering the resist film. This method has a drawback in that the steps such as a resist protective film forming step and a removing step are increased.
- the resist protective film in order not to impair the properties of the resist material, the resist protective film must be "transparent" to radiation such as X-rays and ultraviolet rays used in the resist process.
- the resist protective film composition is also required not to absorb radiation such as X-rays and ultraviolet rays and to cause no side reaction such as insolubilization.
- many of the substances used for resist protective film compositions that have the effect of suppressing the PED effect do not satisfy the above conditions.
- a resist protective film composition that is transparent and sufficiently suppresses the PED effect has not been found so far.
- the immersion exposure technique high-resolution exposure is possible by using a liquid having a large refractive index between the lens and the resist film.
- the resist film swells and impurities generated from the resist film. Is dissolved in the upper liquid and contaminates the lens.
- One method for solving this problem is to apply a resist protective film composition on the resist film that is incompatible with the difference between the liquid having a large refractive index and the resist film and that can further reduce the PED effect described above. A way to do this is desired.
- Patent Document 6 describes that a cyclic or chain perfluoroalkyl polyether is effective as a resist protective film forming material.
- Patent Document 1 Japanese Patent Laid-Open No. 4189880
- Patent Document 2 Japanese Patent Laid-Open No. 4-226177
- Patent Document 3 JP-A-6-220232
- Patent Document 4 International Publication No.02Z064648 Pamphlet
- Patent Document 5 Japanese Patent Laid-Open No. 4-204848
- Patent Document 6 International Publication No. 04Z074937 Pamphlet
- Non-Patent Document 1 S. A. MacDonald et al., Proc. SPIE, Vol. 1466, P2 (1991) Disclosure of the Invention
- the problem to be solved by the present invention is that a fluorine-containing compound, a fluorine-containing polymer, and a production thereof having a high concentration of functional groups and capable of obtaining sufficient functional group characteristics and having high transparency in a wide wavelength range. Is to provide a method. Furthermore, as chemical amplification type resists, far ultraviolet rays such as KrF and ArF excimer lasers and vacuum such as F excimer lasers are used.
- An object of the present invention is to provide a resist composition that provides a resist pattern that is excellent in transparency to ultraviolet rays and dry etching properties, and further excellent in sensitivity, resolution dissolution rate, flatness, and the like. Furthermore, it is to provide a resist protective film composition that protects the resist film from the immersion solvent by the immersion lithography process.
- the present invention provides a fluorine-containing gene represented by the following formulas (1) to (3).
- R 1 is a hydrogen atom, an alkyl group having 20 or less carbon atoms, or (CH 3) 2 CO 2
- OR 4 (a is 0 or 1, R 4 is a hydrogen atom or an alkyl group having 20 or less carbon atoms). When R 1 or R 4 is an alkyl group, some or all of these hydrogen atoms may have an etheric oxygen atom which may be substituted with a fluorine atom.
- R 2 and R 3 each independently represents a hydrogen atom or an alkyl group having 12 or less carbon atoms. R 2 or R 3 When is an alkyl group, some or all of these hydrogen atoms may have an etheric oxygen atom which may be substituted with a fluorine atom.
- R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 12 or less carbon atoms.
- Q 1 is (CH) C (CF) (R 5 ) OR 1 ⁇ is an integer from 0 to 3, c and d are
- R 5 is a hydrogen atom or a methyl group.
- R 1 is a hydrogen atom, an alkyl group having 20 or less carbon atoms, or (CH 3) COOR 4 (a is 0 or 1,
- R 4 represents a hydrogen atom or an alkyl group having 20 or less carbon atoms. ). When R 3 or R 4 is an alkyl group, some or all of those hydrogen atoms may be substituted with fluorine atoms, and may have an etheric oxygen atom.
- R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 12 or less carbon atoms.
- Q 2 is (CH) C (CF) (R 5 ) OR ⁇ b is an integer from 0 to 3, c and d are
- R 5 is a hydrogen atom or a methyl group.
- R 1 is a hydrogen atom, an alkyl group having 20 or less carbon atoms, or (CH 3) COOR 4 (a is 0 or 1,
- the present invention also provides a fluorinated polymer having a monomer unit formed by cyclization polymerization of the fluorinated gen represented by any one of the above formulas (1) to (3).
- the present invention provides a method for producing a fluorine-containing polymer, characterized in that the fluorine-containing gene represented by any one of the above formulas (1) to (3) is cyclized and polymerized.
- the present invention provides a fluorine-containing polymer having a monomer unit formed by cyclization polymerization of a fluorine-containing gen represented by any one of the above formulas (1) to (3), an acid upon irradiation with light.
- the present invention provides a resist composition comprising an acid generating compound capable of generating an organic solvent and an organic solvent.
- the present invention provides a fluorine-containing polymer having a monomer unit formed by cyclopolymerizing a fluorine-containing gen represented by the following formula (14) or a fluorine-containing gen represented by the following formula (15): The And a solvent for dissolving the fluorine-containing polymer.
- R 1 is a hydrogen atom, an alkyl group having 20 or less carbon atoms, or (CH 3) 2 CO 2
- OR 4 (a is 0 or 1, R 4 is a hydrogen atom or an alkyl group having 20 or less carbon atoms). When R 1 or R 4 is an alkyl group, some or all of these hydrogen atoms may have an etheric oxygen atom which may be substituted with a fluorine atom.
- R 2 and R 3 each independently represents a hydrogen atom or an alkyl group having 12 or less carbon atoms. When R 2 or R 3 is an alkyl group, some or all of these hydrogen atoms may have an etheric oxygen atom which may be substituted with a fluorine atom.
- n represents an integer of 0-2.
- R 2 and R 3 each independently represents a hydrogen atom or an alkyl group having 12 or less carbon atoms.
- Q is (CH) C (CF) (R 5 ) 0
- R 5 is a hydrogen atom or a methyl group.
- R 1 is a hydrogen atom, an alkyl group having 20 or less carbon atoms, or (CH 3) COOR 4 (a is 0 or 1, R 4
- R 3 or R 4 is an alkyl group, some or all of these hydrogen atoms may have an etheric oxygen atom which may be substituted with a fluorine atom.
- n represents an integer of 0-2.
- the present invention is a unit derived from a monomer unit obtained by cyclopolymerizing the fluorine-containing gen represented by the above formula (14) or the above formula (15), and represented by the following formula (16):
- R 8 represents an alkyl group having 8 or less carbon atoms.
- the fluorine-containing genide represented by the following formula (14) is a fluorinated gen represented by the following formula (14-1)!
- R 2 , R 3 and n are the same as in formula (14).
- the fluorinated gen represented by the above formula (14-1) is more preferably a fluorinated gen represented by the following formula (14-1-1) or (14-1-2).
- the fluorine-containing copolymer is preferably a fluorine-containing genide represented by the following formula (15): fluorinated gen represented by the following formula (15-1)!
- R 2 , R 3 and n are the same as in formula (14).
- the fluorinated gen represented by the above formula (15-1) is more preferably a fluorinated gen represented by the following formula (15-1-1).
- a butyl ester monomer represented by the above formula (16) is a vinyl ester represented by the following formula (16-1) or (16-2). It is preferable that it is a monomer.
- the present invention is a copolymer of a fluorine-containing gen represented by the above formula (14) or the above formula (15) and a butyl ester monomer represented by the above formula (16).
- a method for producing a fluorine-containing copolymer is provided.
- the present invention also provides a resist protective film composition comprising the above fluorinated copolymer and a solvent for dissolving the fluorinated copolymer.
- the present invention provides a resist film formed on one main surface of a substrate, and a resist protective film is formed on the resist film using the resist protective film composition.
- a resist pattern forming method in which the substrate on which a resist protective film is formed is exposed by an immersion lithography method and developed using an alkaline developer.
- a fluorine-containing polymer having an aliphatic ring structure in the main chain and a functional group in the side chain can be produced.
- the fluorine-containing polymer obtained in the present invention has high chemical stability and heat resistance. It has sex. Since a functional group is introduced into the side chain, sufficient functional group characteristics can be expressed without lowering Tg, which was difficult to achieve with conventional fluorine-containing polymers. Further, it is wide and has high transparency in the wavelength region.
- the resist composition of the present invention can be used as a chemically amplified resist, particularly against far ultraviolet rays such as KrF and ArF excimer lasers and vacuum ultraviolet rays such as F excimer lasers.
- the resist protective film composition of the present invention is particularly useful especially for immersion lithography. That is, the resist protective film composition of the present invention is insoluble in the immersion solvent used in the immersion lithography process and dissolves in the alkaline developer used in the step. Therefore, when the resist protective film composition of the present invention is used, the resist film is prevented from swelling in the immersion lithography process, and the lens is contaminated by dissolving the resist film. Is prevented.
- the fluorinated genes represented by the following formulas (1) to (3) (hereinafter referred to as fluorinated gen (1), fluorinated gen (2) and fluorinated gen It is possible to obtain a fluorine-containing polymer having monomer units formed by cyclopolymerization of
- R 1 is a hydrogen atom, an alkyl group having 20 or less carbon atoms, or (CH 3) 2 CO 2
- OR 4 (a is 0 or 1, R 4 is a hydrogen atom or an alkyl group having 20 or less carbon atoms). When R 1 or R 4 is an alkyl group, some or all of these hydrogen atoms may have an etheric oxygen atom which may be substituted with a fluorine atom.
- R 2 and R 3 each independently represents a hydrogen atom or an alkyl group having 12 or less carbon atoms. When R 2 or R 3 is an alkyl group, some or all of these hydrogen atoms are replaced with fluorine atoms It may have an etheric oxygen atom.
- R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 12 or less carbon atoms.
- Q 1 is (CH) C (CF) (R 5 ) OR 1 ⁇ is an integer from 0 to 3, c and d are
- R 5 is a hydrogen atom or a methyl group.
- R 1 is a hydrogen atom, an alkyl group having 20 or less carbon atoms, or (CH 3) COOR 4 (a is 0 or 1,
- R 4 represents a hydrogen atom or an alkyl group having 20 or less carbon atoms. ). When R 3 or R 4 is an alkyl group, some or all of those hydrogen atoms may be substituted with fluorine atoms, and may have an etheric oxygen atom.
- R 2 and R 3 each independently represents a hydrogen atom or an alkyl group having 12 or less carbon atoms.
- Q 2 is (CH) C (CF) (R 5 ) OR ⁇ b is an integer from 0 to 3, c and d are
- R 5 is a hydrogen atom or a methyl group.
- R 1 is a hydrogen atom, an alkyl group having 20 or less carbon atoms, or (CH 3) COOR 4 (a is 0 or 1,
- R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 12 or less carbon atoms.
- the alkyl group having 12 or less carbon atoms may have a cyclic aliphatic hydrocarbon group consisting of only a linear or branched aliphatic hydrocarbon.
- the alkyl group having 12 or less carbon atoms may have an etheric oxygen atom in which some or all of the hydrogen atoms may be substituted with fluorine atoms.
- the cycloaliphatic hydrocarbon group is preferably a hydrocarbon group having at least one cyclic structure, such as a cyclobutyl group, a cycloheptyl group, a cyclohexyl group as shown below.
- Monocyclic saturated hydrocarbon group bicyclic saturated hydrocarbon group such as 4-cyclohexylcyclohexyl group, polycyclic saturated hydrocarbon group such as 1 decahydronaphthyl group or 2-decahydronaphthyl group, 1 norbornyl group , 1-bridged saturated carbon such as adamantyl group
- Spiro hydrocarbon groups such as hydrogen fluoride groups and spiro [3.4] octyl groups are included.
- R a hydrogen atom, a methyl group, a trifluoromethyl group, or a cyclic aliphatic hydrocarbon group having 6 or less carbon atoms, particularly preferably a hydrogen atom or a methyl group.
- R 2 and R 3 are simultaneously hydrogen atoms.
- d is 1 or 2.
- Fluorine-containing gen (in 3 ⁇ 4, Q 1 is represented by (CH) C (CF) (R 5 ) OR 1 , where
- B is an integer from 0 to 3
- R 5 is a hydrogen atom or a methyl group.
- Q 2 is represented by (CH) C (CF) (R 5 ) OR 1 .
- B is an integer from 0 to 3
- R 5 is a hydrogen atom or a methyl group.
- R 1 is an alkyl group having 20 or less carbon atoms, or (CH 3) COOR 4 , (a is 0 or 1, and R 4 is a hydrogen atom or carbon number 20 or less alkyl
- R 1 or R 4 is an alkyl group, some or all of these hydrogen atoms may have an etheric oxygen atom which may be substituted with a fluorine atom.
- the alkyl group having 20 or less carbon atoms may have a cyclic aliphatic hydrocarbon group consisting of only a linear or branched aliphatic hydrocarbon group.
- a cyclic aliphatic hydrocarbon group the same groups as those described above can be used, and the cyclic structure may have an etheric oxygen atom.
- Specific examples include methyl group, trifluoromethyl group, CH OC H-1, CH OC H, CH
- the (CH 3) COOR 4 is specifically COO (t—CH 2), CH COO (t—CH 2), etc.
- R 4 is an alkyl group having 20 or less carbon atoms
- the alkyl group is a cyclic aliphatic group.
- the number of carbon atoms that may have a hydrocarbon group is preferably 12 or less.
- the cycloaliphatic hydrocarbon group the same groups as described above can be used, and specific examples include the following (in order to clarify the bonding position, it is shown in the form of —OR 4 ) 0 [0043] [Chemical 3]
- R 4 is preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, particularly preferably a hydrogen atom or a t-butyl group.
- R 2 and R 3 are preferably each independently a hydrogen atom or a cyclic aliphatic hydrocarbon group having 6 or less carbon atoms.
- R 1 is a hydrogen atom, carbon An alkyl group having a number of 20 or less, or (CH 3) COOR 4 (a is 0 or 1; R 4 is a hydrogen atom;
- R 2 and R 3 must not be all hydrogen atoms.
- R 3 or R 4 is an alkyl group, part or all of those hydrogen atoms may be substituted with a fluorine atom and may have an etheric oxygen atom.
- the fluorinated gen (1) is more preferably a fluorinated gen represented by the following formula (5) or the following formula (6).
- R 1 is as described above.
- the fluorinated gen (1) is more preferably a fluorinated gen represented by the following formula (7).
- R 2 and R 3 forces are each independently a hydrogen atom or a cyclic aliphatic hydrocarbon group having 6 or less carbon atoms.
- Q 1 is (CH 2) C ( CF) (R 5 )
- R 1 is a hydrogen atom, carbon An alkyl group having a number of 20 or less, or (CH 3) COOR 4 (a is 0 or 1, R 4 is a hydrogen atom or an alkyl having 20 or less carbon atoms
- R 2 and R 3 forces are each independently a hydrogen atom or a cyclic aliphatic hydrocarbon group having 6 or less carbon atoms.
- Q 2 is (CH 2 ) C ( CF) (R 5 )
- R 1 is a hydrogen atom, carbon An alkyl group having a number of 20 or less, or (CH 3) COOR 4 (a is 0 or 1, R 4 is a hydrogen atom or an alkyl having 20 or less carbon atoms
- the oxygen atom may be a methyleneoxy (CH 2 O 3) group so that it can be easily eliminated by an acid. Is particularly preferred to join! / ,.
- R 3 or R 4 is an alkyl group, part or all of the hydrogen atoms may be substituted with a fluorine atom or may have an etheric oxygen atom.
- the fluorinated gen (2) is preferably a fluorinated gen represented by the following formula (8) or (9). In the formula, R 1 is as described above.
- the fluorinated gen (2) is more preferably a fluorinated gen represented by the formula (10).
- Q 3 represents (CH) C (CF) OH (e is 0 or 1).
- the fluorinated gen (3) is preferably a fluorinated gen represented by the following formula (11) or (12).
- R 1 is as described above.
- R 1 is other than a hydrogen atom.
- the fluorinated gen (3) is more preferably a fluorinated gen represented by the formula (13).
- fluorine-containing genes (1) to (3) of the present invention include the following, but are not limited thereto.
- the fluorine-containing polymer of the present invention includes any one of the above-described fluorine-containing genes (1) to (3) of the present invention. It has monomer units formed by cyclopolymerization of these.
- a fluorine-containing polymer having a monomer unit formed by cyclization polymerization of fluorine-containing genus (1) is referred to as a fluorine-containing polymer (A)
- a monomer unit formed by cyclopolymerizing fluorine-containing genus (2) is referred to as a fluorine-containing polymer (A).
- Fluorine-containing polymer (C) is a fluorine-containing polymer having monomer units formed by cyclopolymerization of fluorine-containing genus (3).
- the monomer units of the following (a) to (f) are formed by any cyclopolymerization of the fluorine-containing dienes (1) to (3). It is thought to generate.
- the fluorine-containing polymer (A) has a structure containing the monomer unit (a) or the monomer unit (b). It is considered to have a polymer.
- the fluorine-containing polymer (A) is considered to be a polymer having a structure containing the monomer unit (c).
- the fluoropolymer (B) is considered to be a polymer having a structure containing the monomer unit (f).
- the fluoropolymer (C) is a polymer having a structure containing the monomer unit (d) or the monomer unit (e). it is conceivable that.
- the main chain means a carbon chain composed of four carbon atoms constituting a polymerizable unsaturated bond.
- OR 1 is an acidic group, such as when R 1 is a hydroxyl group
- the acidic group is blocked by alcohols, carboxylic acids, or active derivatives thereof. It may be blocked by reacting with an agent.
- the fluorine-containing polymer is used as a resist composition described later, it is preferable that the OR 1 group that is an acidic group is blocked.
- the active derivative include alkyl halides, acid chlorides, acid anhydrides, chlorocarbonates, dialkyl dicarbonates (such as di-tert-butyl dicarbonate), and 3,4-dihydro-1,2H-pyran. It is done.
- R 1 as the blocked acidic group examples include a methoxymethyl group, an ethoxymethyl group, a 2-methoxyethoxymethyl group, COO (t—CH 2), CH (CH 2) OC H, 2-tetrahydro
- the fluorine-containing polymer of the present invention preferably has an acidic group OR 1 blocked to such an extent that the unexposed portion is not dissolved by the developer. Blocked for this case, the total number of blocks Karitsu (acidic group OR 1 acidic group OR 1 The ratio of OR 1 is 10 to: LOO mol% is preferred, and 10 to 50 mol% is particularly preferred.
- the fluorine-containing polymer (A) of the present invention contains, as an essential component, a monomer unit obtained by cyclopolymerizing the fluorine-containing gene (1), and the fluorine-containing polymer (B) has a ring containing the fluorine-containing polymer (2).
- the fluorine-containing polymer (C) contains a monomer unit obtained by cyclopolymerization of the fluorine-containing diene (3) as an essential component, but the other is within the range without impairing its properties.
- the proportion of other monomer units is preferably 50 mol% or less, particularly preferably 15 mol% or less.
- Fluorine-containing cyclic monomers such as perfluoro (2, 2 dimethyl-1, 3 diquinol), and perfluorogenes such as perfluoro (buturbyl ether) that can undergo cyclopolymerization, hydrated fluorogens, methyl acrylate, ethyl methacrylate
- Acrylic esters such as vinyl esters, vinyl esters having a cyclic structure such as vinyl benzoate and vinyl adamantylate, butyl ethers such as ethyl vinyl ether and cyclohexyl vinyl ether, cyclic olefins such as cyclohexene, norbornene and norbornagen , Anhydrous maleic acid, vinyl chloride and the like.
- a monomer having a blocked acidic group can also be used.
- the molecular weight of the fluoropolymer of the present invention is appropriately selected depending on the application.
- the number average molecular weight in terms of polystyrene is usually 1,000 to 100,000. Is suitable, preferably 2000 to 20,000. If the number average molecular weight is less than 1000, the resulting resist pattern tends to be defective, the remaining film ratio after development is lowered, and the shape stability during pattern heat treatment is liable to occur. If the number average molecular weight exceeds 100,000, the coating properties of the composition may be poor or the developability may be reduced. There is a case to do.
- the polystyrene-equivalent number average molecular weight is usually 1,000 to 100,000, preferably 2000 to 20,000.
- the fluorine-containing polymer (A) of the present invention can be obtained by cyclization polymerization of the fluorine-containing gene (1) under a polymerization initiation source.
- the fluoropolymer (B) of the present invention can be obtained by cyclopolymerizing the fluorogen (2) under a polymerization initiation source.
- the fluoropolymer (C 2) of the present invention can be obtained by cyclopolymerizing the fluorogen (3) under a polymerization initiation source.
- cyclopolymerization in addition to obtaining a homopolymer by cyclopolymerizing one kind of fluorine-containing gens (1) to (3) of the present invention, two or more fluorine-containing polymers Cygenization of gen (1) and copolymerization to obtain a copolymer, and cyclopolymerization of two or more fluorinated gens (2) and copolymerization to obtain a copolymer
- Two or more kinds of fluorinated gens (3) are cyclopolymerized and copolymerized to obtain a copolymer, and any of the fluorinated gens (1) to (3) of the present invention can be used as a ring.
- the polymerization initiation source is not particularly limited as long as it causes the polymerization reaction to proceed radically, and examples thereof include a radical generator, light, and ionizing radiation.
- radical generators that are particularly preferred for radical generators include peracid compounds, azo compounds, and persulfates. Of these, the following peroxides are preferred.
- C H is a phenol group
- C F is a pentafluorophenol group
- C H is a cyclohexyl group
- the polymerization method is not particularly limited, and the monomer is used for polymerization as it is V, so-called Balta polymerization, fluorinated carbonization that can dissolve or disperse fluorine-containing (1) to (3) and other monomers.
- Solution polymerization carried out in hydrogen, chlorohydrocarbon, fluorinated chlorohydrocarbon, alcohol, hydrocarbon, other organic solvents, suspension polymerization carried out in the presence or absence of a suitable organic solvent in an aqueous medium, Examples thereof include emulsion polymerization performed by adding an emulsifier to an aqueous medium.
- the organic solvent used as a solvent in the polymerization is not limited to one type, and may be a mixed solvent of a plurality of types of organic solvents. Specifically, aliphatic hydrocarbons such as pentane, hexane, and heptane, hydrocarbon alcohols such as methanol, ethanol, n -propanol, isopropanol, and t-butanol, acetone, methyl ethyl ketone, and methyl isobutyl ketone.
- aliphatic hydrocarbons such as pentane, hexane, and heptane
- hydrocarbon alcohols such as methanol, ethanol, n -propanol, isopropanol, and t-butanol
- acetone methyl ethyl ketone
- methyl isobutyl ketone methyl isobutyl ketone
- Hydrocarbon ketones such as cyclohexanone, dimethyl ether, jetyl ether, methyl ethyl ether, methylol tert-butylate ethere, hydrocarbon ethers such as diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether, tetrahydrofuran, 1 , 4 Cycloaliphatic hydrocarbon ethers such as dioxane, -Tolyls such as acetonitryl, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, t-butyl acetate, methyl propionate, propio Hydrocarbon esters such as oxyethyl, aromatic hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, R-113, R-113a, R-141b, R—
- the temperature and pressure at which the polymerization is carried out are not particularly limited, but the boiling point of the monomer, the heating source
- a suitable temperature can be set between ⁇ 200 ° C., and a practically suitable temperature can be set at about room temperature to 100 ° C.
- the polymerization pressure may be reduced or increased. Practically, suitable polymerization can be carried out at normal pressure to about 100 atm, and even normal pressure to about 10 atm.
- OR 1 is blocked acidic group, and OR 1 group is-blocked, Do, a fluorine-containing diene by cyclic polymerization, a fluorine-containing polymer After production, the OR 1 group in the fluoropolymer may be blocked with a blocking agent. Or a fluorinated diene which 1 group OR is blocked with a pre-Me blocking agent by cyclic polymerization, Yo be obtained a fluorine-containing polymer OR 1 group is blocked.
- the present invention includes a resist composition comprising fluorine-containing polymers (A) to (C), an acid generating compound (D) that generates an acid upon irradiation with light, and an organic solvent (E). Also provide things.
- the acid generating compound (D) which generates an acid upon irradiation with light in the present invention generates an acid upon exposure. This acid cleaves (deblocks) the blocked acidic groups present in the fluoropolymers (A) to (C). As a result, the exposed portion of the resist film becomes readily soluble in an alkaline developer, and a positive resist pattern is formed by the alkaline developer.
- an acid generating compound used in a normal chemical amplification type resist material can be adopted, such as an olum salt, a halogen-containing compound, Examples thereof include diazo ketone compounds, sulfone compounds, and sulfonic acid compounds.
- Examples of these acid-generating compounds (D) include the following.
- Examples of the salt include ododonium salt, sulfo-salt, phospho-salt, di-salt salt, pyridi-um salt and the like.
- preferred salt include diphenyl rhodium triflate, diphenyl rhodium pyrene sulfonate, diphenyl rhodium dodecyl benzene sulfonate, bis (4-tert-butylphenol) (1) Donium triflate, bis (4-tert-butylphenol) Nsnolephonate, triphenylenores norehonum triflate, triphenylenores norehononium nonate, triphenylsulfo-perfluorooctane sulfonate, triphenenoles norejo
- -Umhexafluoroantimonate 1 (naphthylacetomethyl) thiolaum triflate, cyclohexylmethyl (2-oxocyclohexyl) sulfo-umtriflate, dicyclohexyl (2-oxocyclohexyl) sulfo- Umtriflate, dimethyl (4-hydroxynaphthyl) sulfo-mutosylate, dimethyl (4-hydroxynaphthyl) sulfo-mudecdecylbenzenesulfonate, dimethyl (4-hydroxynaphthyl) sulfo-umuna phthalene sulfonate, triphenylsulfo-umcumphor Examples thereof include sulfonate, (4-hydroxyphenyl) benzylmethylsulfo-toluenesulfonate, and the like.
- halogen-containing compound examples include a haloalkyl group-containing hydrocarbon compound, a haloalkyl group-containing heterocyclic compound, and the like.
- Specific examples include (trichloromethyl) -s triazine derivatives such as phenyl-bis (trichloromethyl) s triazine, methoxyphenyl bis (trichloromethyl) s-triazine, naphthyl bis (trichloromethyl) s triazine, , 1-bis (4 black mouth file) 1, 2, 2 trichrome mouth ethane.
- Examples of the sulfone compound include 13-ketosulfone, 13 sulfonylsulfone, diazo compounds of these compounds, and the like. Specific examples include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenolsulfol) methane, and the like.
- Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, alkyl sulfonic acid imides, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Specific examples include benzoin tosylate and 1,8 naphthalenedicarboxylic imide triflate.
- the acid generator compound (D) can be used alone or in admixture of two or more.
- the organic solvent (E) in the present invention sufficiently dissolves the fluorine-containing polymers (A) to (C) and the acid-generating compound (D), and the solution is applied by spin coating, flow coating,
- the organic solvent is not particularly limited as long as it can be applied by a method such as roll coating to form a uniform coating film.
- Specific examples of the organic solvent (E) include alcohols such as methyl alcohol, ethyl alcohol, diacetone alcohol, acetone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and N-methyl.
- Ketones such as pyrrolidone, ⁇ -butyrolatatone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, carbitol acetate, methyl 3-methoxypropionate, 3-ethoxypropionate Esters such as ethyl onate, methyl ⁇ -methoxyisobutyrate, ethyl butyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, 2-ethoxyethyl acetate, isoamyl acetate, methyl lactate, ethyl lactate, Aromatic hydrocarbons such as ene and xylene, propylene glycol mononomonomethinoatenore, propyleneglycolenomonoethylenotenole, ethyleneglycol mononomonopropinoreino
- organic solvent those exemplified above may be used alone or in combination of two or more kinds. Since the moisture contained in the organic solvent affects the solubility of each component of the resist composition, the coating property to the substrate to be processed, the storage stability, etc., it is preferable that the moisture content is small.
- the proportion of each component in the resist composition of the present invention is usually 0.1 to 20 parts by mass of the acid-generating compound (D) and 100% by mass of the organic solvent E) 50-2000 parts by weight is suitable.
- the acid generating compound (D) is 0.1 to 10 parts by mass and the organic solvent (E) is 100 to 1000 parts by mass with respect to 100 parts by mass of the fluoropolymers (A) to (C).
- the amount of the acid generating compound (D) used is 0.1 parts by mass or more, sufficient sensitivity and developability can be provided, and when it is 10 parts by mass or less, transparency to radiation is sufficient. Thus, a more accurate resist pattern can be obtained.
- the resist composition of the present invention includes an acid-cleavable additive for improving pattern contrast, a surfactant for improving coating properties, and a nitrogen-containing basic for adjusting acid generation pattern.
- an adhesion aid, a storage stabilizer, etc. can be appropriately blended depending on the purpose in order to improve the storage stability of the composition.
- the resist composition of the present invention is preferably used after each component is uniformly mixed and filtered through a 0.1 to 2 m filter.
- a resist film is formed by applying and drying the resist composition of the present invention on a substrate such as a silicon wafer.
- a substrate such as a silicon wafer.
- the coating method spin coating, flow coating, roll coating or the like is adopted.
- Light irradiation is performed through a mask on which a pattern is drawn on the formed resist film, and then development processing is performed to form a pattern.
- the irradiated light is far-field such as g-rays with a wavelength of 436 nm, i-rays with a wavelength of 365 nm, KrF excimer laser with a wavelength of 248 nm, ArF excimer laser with a wavelength of 193 nm, F excimer laser with a wavelength of 157 ⁇ m, etc.
- Examples include ultraviolet rays and vacuum ultraviolet rays.
- This composition is useful for applications where ultraviolet light with a wavelength of 250 nm or less, particularly ultraviolet light with a wavelength of 200 nm or less (ArF excimer laser light or F excimer laser light) is used as a light source.
- the resist composition of the present invention is capable of forming a finer pattern. Applications using an F excimer laser beam as a light source, ArF excimer
- the light source is a light source
- alkaline aqueous solutions are applied as the developing solution.
- alkali include sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, triethylamine and the like.
- the present invention provides a fluorinated polymer having a monomer unit obtained by cyclopolymerizing a fluorinated gen represented by the following formula (14) or (15), and a solvent for dissolving the fluorinated polymer ( F), and a resist protective film composition characterized by comprising:
- R 1 is a hydrogen atom, an alkyl group having 20 or less carbon atoms, or (CH 3) 2 COOR 4 (a
- R 4 represents a hydrogen atom or an alkyl group having 20 or less carbon atoms.
- R 2 and R 3 each independently represents a hydrogen atom or an alkyl group having 12 or less carbon atoms.
- Q is (CH) C (CF) (R 5 ) OR ⁇ R 1 is as described above, b is an integer from 0 to 3, c, d
- R 5 is a hydrogen atom or a methyl group.
- R 3 or R 4 is an alkyl group, some or all of these hydrogen atoms may have an etheric oxygen atom which may be substituted with a fluorine atom.
- n represents an integer of 0-2.
- the fluorine-containing polymer used in the resist protective film composition of the present invention can be widely selected from the above-mentioned fluorine-containing polymers (A) to (C). A range power wider than the contents may be selected.
- n an integer of 0-2.
- the fluorine-containing polymer used in the resist protective film composition of the present invention further includes a monomer unit obtained by cyclopolymerizing a fluorine-containing gen (2 ') represented by the following formula (2'). It may be a fluorine-containing polymer ( ⁇ ') which is a fluorine-containing polymer having.
- R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 12 or less carbon atoms.
- R 5 is a hydrogen atom or a methyl group.
- R 1 is a hydrogen atom, an alkyl group having 20 or less carbon atoms, or (CH 3) COOR 4 (a is 0 or 1, R 4 is hydrogen
- R 3 or R 4 is an alkyl group, some or all of these hydrogen atoms may have an etheric oxygen atom which may be substituted with a fluorine atom.
- These fluoropolymers (C) have a problem of solubility in a basic developer when used in resist yarns and compositions, but the resist protective film is thinner than the resist film. When used in a film composition, the solubility in a basic developer is sufficient.
- the fluorine-containing genes (1) and (3) include those shown below in addition to those shown above as specific examples.
- CF 2 CFCF 2 CCH 2
- the solvent (F) in the present invention is not particularly limited as long as it dissolves a fluorine-containing polymer that can be used in the resist protective film composition of the present invention.
- Alcohols such as methyl alcohol and ethyl alcohol, ketones such as acetone, methyl isobutyl ketone and cyclohexanone, acetates such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as toluene and xylene, propylene glycol monomethyl Glycol monoalkyl ethers such as ether, propylene glycol monoethyl ether, glycol monoalkyl ether esters such as propylene glycol monomethyl ether acetate and carbitol acetate, fluorocarbon, nodular fluorocarbon, nodular fluorocarbon Fluorinated solvents such as fluorocarbons such as fluorocarbons, perfluoroethers, fluoroalcohols, fluorok
- the proportion of each component in the resist protective film composition of the present invention is usually from 50 parts by weight of solvent (F) to 100 parts by weight of fluorine-containing polymer.
- the solvent (F) is preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the fluorine-containing polymer.
- the present invention also provides a fluorine-containing copolymer that is preferably used in a resist protective film composition.
- the fluorine-containing copolymer of the present invention is represented by a unit derived from a monomer unit obtained by cyclopolymerizing a fluorine-containing gen represented by the above formula (14) or (15), and the following formula (16). And a unit derived from a monomer unit obtained by polymerization of a vinyl ester monomer (hereinafter referred to as monomer (16)).
- R 8 is an alkyl group having 8 or less carbon atoms, preferably a methyl group or an ethyl group.
- the fluorinated gen represented by the formula (14) is preferably a fluorinated gen represented by the following formula (14-1).
- the fluorinated gen (14-1) is more preferably a fluorinated gen represented by the following formulas (14-1-1) to (14-1-3).
- a fluorine-containing gen represented by the formula (14-1-1) or (14-1-2) is particularly preferable.
- the fluorinated gen represented by the formula (15) is preferably a fluorinated gen represented by the following formula (15-1).
- the fluorine-containing gen represented by the formula (15) is more preferably a fluorine-containing gen represented by the following formulas (15-1-1) to (15-2-3).
- a fluorine-containing gen represented by the formula (15-1-1) is particularly preferable.
- the monomer (16) is preferably a vinyl ester monomer represented by the following formulas (16-1) to (16-6).
- vinyl ester monomers represented by the formula (16-1) or (16-2) are particularly preferable.
- the fluorine-containing copolymer of the present invention is obtained by polymerizing a unit derived from a monomer unit obtained by cyclopolymerizing fluorine-containing (14) or fluorine-containing (15) and the monomer (16). And a unit derived from a monomer unit as an essential component.
- the proportion of monomer units obtained by polymerizing the monomer (16) is preferably 75 mol% or less, particularly preferably 50 mol% or less. When it is 50 mol% or less, the solubility in a developer is particularly good.
- any of the following monomer units is considered to be formed by the cyclopolymerization of a suitable fluorinated gen (14-1).
- the fluorine-containing copolymer has a structure containing a monomer unit () or a monomer unit (1). It is considered a polymer (hereinafter referred to as copolymer (A)).
- the fluorine-containing copolymer is a copolymer having a structure containing the monomer unit (g), the monomer unit (h) or the monomer unit (i) (hereinafter, Copolymer (B) t).
- the fluorinated copolymer is a copolymer having a structure containing a monomer unit () (hereinafter referred to as copolymer (C) t). It is conceivable that.
- the main chain of the above-described copolymers (A) to (C) constitutes a polymerizable unsaturated double bond.
- any of the following monomer units is considered to be formed by the cyclopolymerization of a suitable fluorinated gen (15-1).
- the fluorinated copolymer has a structure containing monomer unit (j) or monomer unit (k). It is considered that it has a copolymer (hereinafter referred to as copolymer (D)).
- the fluorinated copolymer is a copolymer having a structure containing the monomer unit (1), the monomer unit (m) or the monomer unit (n) (hereinafter, Copolymer (E) t )it is conceivable that.
- the fluorine-containing copolymer is considered to be a copolymer having a structure containing the monomer unit (o) (hereinafter referred to as copolymer (F)). .
- the main chains of the above-mentioned copolymers (D) to (F) are carbon chains composed of carbon atoms constituting a polymerizable unsaturated bond.
- the acidic hydroxyl group concentration in the fluorinated copolymer can be changed by adjusting the proportion of the monomer (16), the solubility in a developer when used in a resist protective film composition is also possible. And the balance of interaction between the immersion medium and water can be optimized. Furthermore, since the unit derived from the monomer unit obtained by polymerizing the monomer (16) has a polar group such as a carbonyl group, a resist protective film composition using a fluorine-containing copolymer Compared with a resist protective film composition using a homopolymer, adhesion to a substrate such as a silicon wafer or a resist film is improved.
- a unit derived from a monomer unit obtained by cyclopolymerization of fluorine-containing gen (14) or fluorine-containing gen (15) and monomer (16) are polymerized.
- the proportion of the other monomer units preferably preferably 50 mol% or less implement particular 15 mole 0/0 or less.
- those exemplified in [0073] to [0076] can be used.
- the fluorine-containing copolymer of the present invention is obtained by copolymerizing a fluorine-containing gen (14) or fluorine-containing gen (15) and a monomer (16) under a polymerization initiation source. .
- Fluorine-containing poly When the monomer (16) contains a monomer unit derived from another monomer, the other monomer is also copolymerized.
- the polymerization initiation source, organic solvent, copolymerization conditions, etc. used in the copolymerization are the same as those in [0079] to [0082].
- the present invention provides a resist protective film composition
- a resist protective film composition comprising the above-mentioned fluorine-containing copolymer and a solvent that dissolves the fluorine-containing copolymer.
- the solvent for dissolving the fluorine-containing copolymer and the ratio of each component are the same as those in [0100] to [0101].
- the solvent is a solvent that does not dissolve the resist film. Fluoroethers, fluoroalcohols, and fluoroketones are particularly preferred.
- the resist protective film composition of the present invention is preferably used after the components are uniformly mixed and then filtered through a filter having a pore size of 0.1 to 2 m! /.
- a resist protective film is formed by applying and drying the resist protective composition of the present invention on a resist film on a substrate such as a silicon wafer.
- a coating method spin coating, flow coating, roll coating or the like is adopted. Light irradiation is performed through a mask on which a pattern is drawn on the formed resist protective film, and then development processing is performed, and the resist protective film is removed to form a resist film pattern.
- the resist protective film composition of the present invention can be widely used for the purpose of protecting the resist film in the lithographic process. However, it is preferably used in the same manner as the immersion lithography used to improve the resolution.
- an immersion liquid such as an organic compound solution containing water or other fluorine atoms is placed between the irradiation light source (actually the focus lens of the light source irradiation device) and the resist film. And improve the resolution by using the refractive index. For this reason, when the immersion lithography process is used, the resist film is swollen or the free components from the resist film are eluted into the immersion liquid. May be contaminated.
- the protective film formed from the resist protective film composition of the present invention is insoluble in an immersion liquid such as water and soluble in a developer, the resist film swells in the course of immersion lithography, resist film This eliminates the possibility of contamination of the lens by free components from the lens.
- the resist protective film composition of the present invention is most preferably used in an immersion lithographic process using water as an immersion liquid and using an ArF excimer laser beam as a light source.
- the resist film to which the protective film composition of the present invention is applied is not particularly limited, and widely includes those used in conventional lithographic processes.
- the light emitted in the lithographic process includes ultraviolet rays such as g-line with a wavelength of 436 nm, i-line with a wavelength of 365 nm, KrF excimer laser with a wavelength of 248 nm, ArF excimer laser with a wavelength of 193 nm, and F excimer laser with a wavelength of 157 nm.
- ultraviolet rays such as g-line with a wavelength of 436 nm, i-line with a wavelength of 365 nm, KrF excimer laser with a wavelength of 248 nm, ArF excimer laser with a wavelength of 193 nm, and F excimer laser with a wavelength of 157 nm.
- the resist protective film composition of the present invention uses ultraviolet light having a wavelength of 250 nm or less, particularly ultraviolet light having a wavelength of 200 nm or less (ArF excimer laser light or F excimer laser light) as a light source.
- the present invention provides a resist film formed on one main surface of a substrate, a resist protective film is formed on the resist film using the resist protective film composition, and then the substrate is immersed in the liquid.
- a method of forming a resist pattern which is exposed by lithography and is alkali-developed.
- the material used for forming the resist film is not particularly limited, and it is preferable to use the resist composition of the present invention as described above.
- the method of forming this resist film on one main surface of the substrate is not particularly limited, but is the same as described above, and is a method of applying and drying on a substrate such as a silicon wafer by spin coating, flow coating, roll coating or the like. Can be illustrated.
- the resist protective film is formed using the resist protective film composition of the present invention.
- a resist protective film By forming a resist protective film using the resist protective film composition of the present invention, elution of an acid generator or the like from the resist film into an immersion medium can be suppressed, and a fine resist pattern can be formed.
- the method for forming this resist protective film on the resist film is particularly limited. However, it is the same as described above, and examples thereof include a method of applying and drying on the resist film by spin coating, flow coating, roll coating or the like.
- the method of exposing the substrate on which the resist film and the resist protective film are formed by the immersion lithography method and performing alkali development is the same as described above.
- An immersion liquid such as an organic compound solution containing water or other fluorine atoms is placed between the irradiation light source (actually, the light source is the focus lens of the light source irradiation device) and the resist film, and the refractive index of these is set. Use this size to improve resolution.
- Various alkaline aqueous solutions are used as the alkali developer used for alkali development, and examples thereof include sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, and triethylamine.
- the light used in this immersion lithography method is not particularly limited, and excimer lasers such as KrF and ArF can be used.
- THF tetrahydrofuran. PSt; polystyrene. R225; dichloropentafluoropropane (solvent).
- PFB Perfluorobutyryl peroxide.
- PFBPO Perfluorobenzoyl peroxide.
- IPP diisopropyl peroxydicarbonate.
- BPO benzoyl peroxide.
- 850 ml of 1M THF solution of Br was added dropwise after about 1.5 hours. After completion of the dropwise addition, the mixture was stirred at 0 ° C for 60 minutes and at room temperature for 16 hours. To this solution, 850 ml of 1N hydrochloric acid was added dropwise and allowed to stand to separate the reaction solution into two layers. The upper organic layer is collected and concentrated with an evaporator, and then low-boiling components are removed by distillation under reduced pressure to obtain 234 g of CF C1CFC1CF C (CF) (OH)
- FC1CF C (CF) (OCH OCH) CH CH Crude liquid 108g was dripped over 1 hour, continuously
- FC (CF) (OCH OCH) CH CH (49 ° C / 1.5 kPa, hereinafter referred to as “monomer 2”)
- the reaction was carried out in the same manner as in Example 4 except that 2M THF solution of CHCH CH MgCl was used.
- CH CHMgCl instead of 2M THF solution
- CH CHCH CH M
- PFB ZR225 solution an R225 solution containing 3 wt% PFB as a polymerization initiator
- polymer 1A-1 an amorphous polymer having a fluorine-containing ring structure in the main chain
- PSt polystyrene
- Mn number average molecular weight
- Mw weight average molecular weight
- MwZMn 2.19. It was.
- Tg was 86 ° C.
- the polymer was a white powder at room temperature.
- the obtained polymer was soluble in acetone, THF, ethyl acetate, methanol, 2-perfluorohexylethanol, and soluble in R225, perfluoro (2-butyltetrahydrofuran), and perfluoro-n-octane.
- Tg was 83 ° C.
- the polymer was a white powder at room temperature.
- the obtained polymer was soluble in acetone, THF, ethyl acetate, methanol, 2-perfluorohexylethanol, and insoluble in R225, perfluoro (2-butyltetrahydrofuran), and perfluoro-n-octane.
- polymer 2A an amorphous polymer having a fluorinated ring structure in the main chain
- Tg When measured by differential scanning calorimetry (DSC), Tg was 91.8 ° C., and it was a white powdery polymer at room temperature.
- the polymer composition calculated by 19 F-NMR and 1 H-NMR measurements was as follows: repeating unit consisting of monomer 1 Z repeating unit consisting of monomer 2 84 416 mol%.
- the obtained polymer was soluble in acetone, THF, ethyl acetate, and methanol, and insoluble in R225, perfluoro (2-butyltetrahydrofuran), and perfluoro-n-octane.
- polymer 1B an amorphous polymer having a fluorine-containing ring structure in the main chain
- Tg was 169 ° C when measured by differential scanning calorimetry (DSC). It was a white powdery polymer at room temperature.
- the obtained polymer was soluble in acetone, THF, ethyl acetate, methanol, 2-perfluorohexylethanol, and insoluble in R225, perfluoro (2-butyltetrahydrofuran), and perfluoro-n-octane.
- Example 11 the reaction was carried out in the same manner as in Example 11 except that monomer 3 obtained in Example 2 was used instead of monomer 1 and monomer 4 obtained in Example 3 was used instead of monomer 2.
- polymer 2B an amorphous polymer having a fluorine-containing ring structure
- Synthesis Example 3 the reaction was conducted in the same manner as in Synthesis Example 3 except that monomer 5 obtained in Example 4 was used instead of monomer 1, and an amorphous polymer having a fluorinated ring structure in the main chain ( Hereinafter, referred to as “polymer 1C”). It was a white powder polymer at room temperature, soluble in acetonitrile, THF, and methanol, and insoluble in R225, perfluoro (2-butyltetrahydrofuran), and perfluoro-n-octane.
- Synthesis Example 3 the reaction was conducted in the same manner as in Synthesis Example 3 except that monomer 6 obtained in Example 5 was used instead of monomer 1, and an amorphous polymer having a fluorinated ring structure in the main chain ( Hereinafter, “polymer 1D” was obtained. It was a white powder polymer at room temperature, soluble in acetonitrile, THF, and methanol, and insoluble in R225, perfluoro (2-butyltetrahydrofuran), and perfluoro-n-octane.
- Example 11 the reaction was carried out in the same manner as in Example 11 except that the monomer 5 obtained in Example 4 was used instead of the monomer 1, and the monomer 7 obtained in Example 6 was used instead of the monomer 2.
- An amorphous polymer having a fluorine-containing ring structure (hereinafter referred to as “polymer 2C”) can be obtained. [0150] (Example 17)
- Example 11 the reaction was carried out in the same manner as in Example 11 except that the monomer 6 obtained in Example 5 was used instead of the monomer 1 and the monomer 8 obtained in Example 7 was used instead of the monomer 2, and the main chain was used.
- An amorphous polymer having a fluorine-containing ring structure (hereinafter referred to as “polymer 2D”) can be obtained.
- Synthesis Example 3 the reaction was performed in the same manner as in Synthesis Example 3 except that the monomer 9 obtained in Synthesis Example 2 was used instead of Monomer 1, and an amorphous polymer having a fluorinated ring structure in the main chain ( Hereinafter, “polymer 1E” was obtained. It was a white powder polymer at room temperature, soluble in acetonitrile, THF, and methanol, and insoluble in R225, perfluoro (2-butyltetrahydrofuran), and perfluoro-n-octane.
- Synthesis Example 3 the reaction was conducted in the same manner as in Synthesis Example 3 except that the monomer 10 obtained in Example 8 was used instead of the monomer 1, and an amorphous polymer having a fluorinated ring structure in the main chain (hereinafter referred to as “monomeric polymer”). And “polymer 1F”). It was a white powdery polymer at room temperature, soluble in acetone, THF, methanol, and insoluble in R225, perfluoro (2-butyltetrahydrofuran), and perfluoro-n-octane.
- Example 11 the reaction was conducted in the same manner as in Example 11 except that monomer 9 obtained in Synthesis Example 2 was used instead of monomer 1 and monomer 11 obtained in Example 9 was used instead of monomer 2.
- An amorphous polymer having a fluorine-containing ring structure (hereinafter referred to as “polymer 2E”) can be obtained.
- Example 11 the reaction was carried out in the same manner as in Example 11 except that monomer 10 obtained in Example 8 was used instead of monomer 1 and monomer 12 obtained in Example 10 was used instead of monomer 2.
- An amorphous polymer having a fluorine-containing ring structure in the main chain (hereinafter referred to as “polymer 2F”) can be obtained.
- polymer 3A adamantylmethoxymethyl
- polymer 3C methylated polymer
- polymer 3D methylated polymer
- polymer 3E methylated polymer
- polymer 3F methylated polymer
- Tg When measured by differential scanning calorimetry (DSC), Tg was 133 ° C., and the polymer was a white powder at room temperature.
- the polymer composition calculated by 19 F—NMR and 1 H—NMR measurement is the repeating unit consisting of monomer 2 / 1,1,2,3,3 pentafluoro-4 4-hydroxy-1 4 trifluoromethyl-1, The repeating unit consisting of 6-hexabutadiene was 89 Zll mol%.
- the obtained polymer was soluble in acetone, THF, ethyl acetate, methanol, 2-perfluorohexylethanol, and insoluble in perfluoro (2-butyltetrahydrofuran) and perfluorooctane.
- polymer 1H an amorphous polymer having a fluorine-containing ring structure in the main chain
- the obtained polymer was soluble in acetone, THF, ethyl acetate, and methanol, and insoluble in R225, perfluoro (2-butyltetrahydrofuran), and perfluoro-octane.
- Polymer 1H obtained in the same manner as in Synthesis Example 6 2.24g and methanol 47g 200ml In a glass flask. To this solution was added 2.18 g of methanolic sodium hydroxide (4.1%) and stirred at room temperature for 12 hours. The reaction solution was concentrated in an evaporator, Methanol was removed by vacuum drying, and 60 g of THF was added to the obtained polymer powder, and then 0.35 g of chloromethyl methyl ether was added and stirred at room temperature.
- Tg was 151 ° C.
- the polymer was a white powder at room temperature. From 19 F-NMR and 1 H-NMR measurements, it was found that 20.5% of the hydroxyl groups in this polymer were methoxymethyl etherified. The obtained polymer was soluble in acetone, THF, ethyl acetate, and methanol, and insoluble in R225, perfluoro (2-butyltetrahydrofuran), and perfluoro-n-octane.
- polymer U an amorphous polymer having a fluorine-containing ring structure in the main chain
- Mn number average molecular weight
- Mw weight average molecular weight
- MwZMn 2.63.
- Tg was 145 ° C.
- the polymer was a white powder at room temperature.
- 19 F- been port Rimmer composition calculated by NMR and 1 H- NMR measurement was repeated units 79Z14Z7 mole 0/0 comprising repeating units Z monomer 2 comprising repeating units / monomer 14 consisting of monomers 13.
- the obtained polymer was soluble in acetone, THF, ethyl acetate, and methanol, and insoluble in R225, perfluoro (2-butyltetrahydrofuran), and perfluoro-n-octane.
- polymer 1K an amorphous polymer having a fluorine-containing ring structure in the main chain
- Tg 126 ° C.
- the polymer was a white powder at room temperature.
- the obtained polymer was soluble in acetone, THF, ethyl acetate, and methanol, and insoluble in R225, perfluoro (2-butyltetrahydrofuran), and perfluoro-n-octane.
- polymer 1L an amorphous polymer having a fluorine-containing ring structure in the main chain
- polymer 1L 1.2 Og
- the obtained polymer was soluble in acetone, THF, ethyl acetate, and methanol, and insoluble in R225, perfluoro (2-butyltetrahydrofuran), and perfluoro-octane.
- polymer 1M an amorphous polymer having a fluorine-containing cyclic structure in the main chain
- the Tg measured by differential scanning calorimetry (DSC) was 152 ° C., and the polymer was a white powder at room temperature. The obtained polymer was soluble in acetone, THF, ethyl acetate, methanol, R225, and insoluble in hexane.
- polymer 1N an amorphous polymer having a fluorine-containing ring structure in the main chain
- the Tg measured by differential scanning calorimetry (DSC) was 118 ° C, and the polymer was a white powder at room temperature.
- the obtained polymer was soluble in acetone, THF, ethyl acetate, methanol, R225, and insoluble in hexane.
- the polymers 1A-1, 1, 2A, 1M and 1N synthesized in Synthesis Example 3, Example 11, Synthesis Example 7, and Synthesis Example 8 were dissolved in 10 g of 2-heptanone, and PTFE (with a pore size of 0.
- a resist protective film composition was produced by filtration using a polytetrafluoroethylene) filter.
- the above-mentioned resist protective film composition was spin-coated on a silicon substrate, followed by heat treatment at 100 ° C. for 90 seconds to form a resist protective film having a thickness of 0.20 / zm.
- the light transmittance of the resist protective film thus obtained is shown in Table 1.
- a PTFE filter having a pore size of 0.2 ⁇ was prepared by dissolving 0.7 g of each of the polymers 2A and 1G synthesized in Example 11 and Example 27 and 0.035 g of triphenylsulfur triflate in 10 g of 2-heptanone. was filtered to prepare a resist composition.
- the above resist composition is spin-coated on a silicon substrate and heated at 100 ° C for 90 seconds after coating.
- a resist film having a thickness of 0.20 / zm was formed by processing.
- the light transmittance of the resist film thus obtained is shown in Table 2.
- the resist protective film composition described above was spin-coated on a silicon substrate treated with hexamethyldisilazane, and after the coating, heat-treated at 100 ° C. for 90 seconds to obtain a film thickness of 0.15 / X m.
- a strike protective film was formed.
- the contact angle of the resist protective film thus obtained with respect to water was measured. The results are shown in Table 3.
- the resist protective film on the silicon substrate prepared in Examples 38 to 40 was immersed in water and alkaline developer for 30 seconds. Thereafter, the film was dried at 110 ° C. for 90 seconds, and the change in film thickness before and after immersion in water and an alkaline image solution was measured. The results are shown in Table 4.
- the polymers 1A-1, 1M, and IN 1g synthesized in Synthesis Example 3, Synthesis Example 7, and Synthesis Example 8 were dissolved in 10 g of 2-heptanone and filtered using a PTFE filter having a pore size of 0.2 m. Thus, a resist protective film composition was produced.
- the above-mentioned resist protective film composition was spin-coated on a silicon substrate, followed by heat treatment at 100 ° C. for 90 seconds to form a resist protective film having a thickness of 0.20 / zm.
- the refractive index of the resist protective film thus obtained was measured with a spectroscopic ellipsometer (M2000D) manufactured by J.A. The results are shown in Table 5.
- a solution obtained by further diluting 200 ml of the solution with 200 ml of dehydrated THF was added dropwise over about 5.5 hours. After completion of dropping, the mixture was stirred at 0 ° C for 30 minutes and at room temperature for 17 hours, and 200 ml of 2N hydrochloric acid was added dropwise. 200 ml of water and 300 ml of jetyl ether were vigorously separated to obtain a jetyl ether layer as an organic layer. The organic layer was dried over magnesium sulfate and then filtered to obtain a crude liquid. The crude liquid was concentrated with an evaporator and then distilled under reduced pressure to obtain 85 g of CF C1CFC1CF C (CF) (OH) CH CH CH
- a glass pressure-resistant reactor having an internal volume of 30 mL was charged with 5.0 g of the monomer 15 obtained in Synthesis Example 9, 0.35 g of butyl acetate, and 18.2 g of ethyl acetate.
- 0.35 g of IPP was added as a polymerization initiator.
- the system was degassed under reduced pressure and then polymerized in a thermostatic chamber (40 ° C) for 18 hours. After the polymerization, the reaction solution was dropped into hexane to reprecipitate the polymer, followed by vacuum drying at 110 ° C. for 24 hours.
- polymer 5A an amorphous polymer having a fluorine-containing ring structure in the main chain
- Tg was not detected by differential scanning calorimetry (DSC). It was a white powdery polymer at room temperature.
- the resulting polymer is soluble in acetone, THF, ethyl acetate, and methanol, but insoluble in R225, perfluoro (2-butyltetrahydrofuran), and perfluoro-octane. Met.
- a glass pressure-resistant reactor having an internal volume of 30 mL was charged with 3.0 g of monomer 1 obtained in Synthesis Example 1, 0.43 g of butyl acetate, and 13.7 g of ethyl acetate.
- 0.257 g of IPP was added as a polymerization initiator. After degassing the inside of the system under reduced pressure, polymerization was carried out in a thermostatic chamber (40 ° C) for 18 hours. After the polymerization, the reaction solution was dropped into hexane to reprecipitate the polymer, followed by vacuum drying at 90 ° C. for 24 hours.
- polymer 6A an amorphous polymer having a fluorine-containing ring structure in the main chain
- a glass pressure-resistant reactor having an internal volume of 30 mL was charged with 3.0 g of monomer 1 obtained in Synthesis Example 1, 1.01 g of vinyl acetate, and 16. Og of ethyl acetate.
- 0.301 g of IPP was added as a polymerization initiator. After degassing the inside of the system under reduced pressure, polymerization was carried out in a thermostatic chamber (40 ° C) for 18 hours. After the polymerization, the reaction solution was dropped into hexane to reprecipitate the polymer, followed by vacuum drying at 80 ° C. for 24 hours.
- polymer 6B an amorphous polymer having a fluorine-containing ring structure in the main chain
- Tg was 86 ° C as measured by differential scanning calorimetry (DSC), and the polymer was a white powder at room temperature.
- polymer 6C an amorphous polymer having a fluorine-containing ring structure in the main chain
- Tg was 82 ° C as measured by differential scanning calorimetry (DSC), and the polymer was a white powder at room temperature.
- the obtained polymer was soluble in acetone, THF, ethyl acetate, methanol and R225, but insoluble in perfluoro (2-butyltetrahydrofuran) and perfluoro-n-octane.
- a glass pressure-resistant reactor having an internal volume of 30 mL was charged with 2.0 g of monomer 1 obtained in Synthesis Example 1, 1.82 g of butyl propionate, and 15.3 g of ethyl acetate. Next, 0.287 g of IPP was added as a polymerization initiator. The system was degassed under reduced pressure and then polymerized in a thermostatic chamber (40 ° C) for 18 hours. After the polymerization, the reaction solution was dropped into hexane to reprecipitate the polymer, followed by vacuum drying at 80 ° C. for 24 hours.
- polymer 6D an amorphous polymer having a fluorine-containing ring structure in the main chain
- the obtained polymer was soluble in acetone, THF, ethyl acetate, methanol and R225, but insoluble in perfluoro (2-butyltetrahydrofuran) and perfluoro-n-octane.
- Example 54 A glass pressure-resistant reactor having an internal volume of 30 mL was charged with 2.0 g of monomer 16 obtained in Synthesis Example 10, 0.23 g of butyl acetate, and 8.9 g of ethyl acetate. Next, 0.168 g of PFBPO was added as a polymerization initiator. The system was degassed under reduced pressure, and then polymerized in a constant temperature shaking tank (70 ° C) for 18 hours. After the polymerization, the reaction solution was dropped into hexane to reprecipitate the polymer, followed by vacuum drying at 90 ° C for 24 hours.
- polymer 7A an amorphous polymer having a fluorinated ring structure in the main chain
- Tg was 102 ° C as measured by differential scanning calorimetry (DSC), and the polymer was a white powder at room temperature.
- the obtained polymer was soluble in acetone, THF, ethyl acetate, methanol and R225, but insoluble in perfluoro (2-butyltetrahydrofuran) and perfluoro-n-octane.
- polymer 7B an amorphous polymer having a fluorine-containing ring structure in the main chain
- Tg was 83 ° C as measured by differential scanning calorimetry (DSC), and the polymer was a white powder at room temperature.
- the obtained polymer was soluble in acetone, THF, ethyl acetate, methanol and R225, but insoluble in perfluoro (2-butyltetrahydrofuran) and perfluoro-n-octane.
- Example 56 to 61 Each of the polymers 5A, 6B, 6C, 6D, 7A, and 7B obtained in Examples 49, 51, 52, 53, 54, and 55 1. Og is referred to as propylene glycol monomethyl ether acetate (hereinafter “PEGM EA”). ) To give a 10% solution. Next, the mixture was filtered using a PTFE filter having a pore diameter of 0.2 i um to produce a resist protective film composition.
- PEGM EA propylene glycol monomethyl ether acetate
- the resist protective film composition described above was spin-coated on a CaF substrate, followed by heat treatment at 100 ° C. for 90 seconds to form a resist protective film.
- the CaF substrate on which the resulting resist protective film was formed was placed in a nitrogen-substituted transmittance measuring device (spectrometer KV-201AD type extreme ultraviolet spectroscopic measuring device), and the light transmittance at 157 nm and 193 nm was measured. .
- the results are shown in Table 6.
- a resist protective film composition prepared in Examples 57, 58, and 61 was spin-coated on a silicon substrate, and after the coating, heat-treated at 100 ° C for 90 seconds to form a resist protective film, manufactured by JAWoollam
- the refractive index for light of 193 nm was measured with a spectroscopic ellipsometer (M2000D). The results are shown in Table 7.
- the polymers obtained in Examples 49-55 were dissolved in PEGMEA to make a 10% solution. Next, this was filtered using a PTFE filter having a pore diameter of 0.2 m, the above polymer solution was spin-coated on a silicon substrate, and further heat-treated at 100 ° C for 90 seconds to obtain a film thickness. A 0.2 m polymer film was formed and the static contact angle with water was measured. The results are shown in Table 9.
- the polymers obtained in Examples 49-55 were dissolved in PEGMEA to make a 10% solution. Next, this was filtered using a PTFE filter having a pore diameter of 0.2 m, the above polymer solution was spin-coated on a quartz resonator, and further heated at 100 ° C for 90 seconds to form a membrane. A 0.2 m thick polymer thin film was formed. Next, the quartz crystal -Umhide mouth oxide 2. Immerse in 38% aqueous solution (hereinafter referred to as “TMAH solution”) and use the quartz crystal microbalance (QCM) method to dissolve the polymer in the soot solution (hereinafter referred to as “development speed”). ”) was measured. The results are shown in Table 10.
- the polymer 6A obtained in Example 50 was dissolved in n-butanol to obtain a 1.0% solution (hereinafter referred to as “protective film composition 6AP”).
- Resist HP AR715 manufactured by Sumitomo Chemical Co., Ltd. is spin-coated on a silicon substrate treated with an organic anti-reflective coating (BARC), and then heat-treated at 130 ° C for 60 seconds to form a resist film with a thickness of 150 nm. (Hereinafter referred to as “wafer IX”) o Next, the resist film on the silicon substrate was further spin-coated with the protective film composition 6AP to form a resist protective film having a thickness of 30 nm (hereinafter referred to as “wafer 1Y”). ""
- the wafers IX and 1Y were subjected to a 90nmL / S exposure test in dry and immersion (immersion medium: ultrapure water) using a two-beam interference exposure apparatus using a laser beam with a wavelength of 193nm.
- the shapes were compared with SEM images. The results are shown in Table 11.
- the processing conditions after exposure are as follows.
- the fluorine-containing polymer of the present invention can be used as a base polymer for a photoresist and a polymer for a resist protective film, for example, an ion exchange resin, an ion exchange membrane, a fuel cell, various battery materials, an optical fiber, and an electronic member. It can be used for transparent film materials, agricultural film films, adhesives, textile materials, weather-resistant paints, etc.
- the Japanese Patent Application 2004-223363 filed on July 30, 2004, the Japanese Patent Application 2004-340595 filed on November 25, 2004, and the May 24, 2005 application The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2005-151028 are hereby incorporated herein by reference as the disclosure of the specification of the present invention.
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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EP05766146A EP1772468A4 (en) | 2004-07-30 | 2005-07-22 | FLUORINE-CONTAINING COMPOUND, FLUORINE-CONTAINING POLYMER, RESIST COMPOSITION, AND RESISTANT PROTECTIVE FILM COMPOSITION |
JP2006529303A JPWO2006011427A1 (ja) | 2004-07-30 | 2005-07-22 | 含フッ素化合物、含フッ素ポリマー、レジスト組成物、およびレジスト保護膜組成物 |
US11/626,913 US7498393B2 (en) | 2004-07-30 | 2007-01-25 | Fluorinated compound, fluoropolymer, resist composition, and composition for resist protective film |
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JP2004-223363 | 2004-07-30 | ||
JP2004223363 | 2004-07-30 | ||
JP2004-340595 | 2004-11-25 | ||
JP2004340595 | 2004-11-25 | ||
JP2005151028 | 2005-05-24 | ||
JP2005-151028 | 2005-05-24 |
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US11/626,913 Continuation US7498393B2 (en) | 2004-07-30 | 2007-01-25 | Fluorinated compound, fluoropolymer, resist composition, and composition for resist protective film |
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EP (1) | EP1772468A4 (ja) |
JP (1) | JPWO2006011427A1 (ja) |
KR (1) | KR20070038533A (ja) |
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EP1679297A1 (en) * | 2003-10-31 | 2006-07-12 | Asahi Glass Company Ltd. | Fluorine compound, fluoropolymer, and process for producing the same |
JP2006337811A (ja) * | 2005-06-03 | 2006-12-14 | Matsushita Electric Ind Co Ltd | バリア膜形成用材料及びそれを用いたパターン形成方法 |
WO2007029765A1 (ja) * | 2005-09-09 | 2007-03-15 | Tokyo Ohka Kogyo Co., Ltd. | 保護膜形成用材料およびこれを用いたホトレジストパターン形成方法 |
JP2007208022A (ja) * | 2006-02-02 | 2007-08-16 | Sokudo:Kk | 基板処理装置および基板処理方法 |
EP1821148A2 (en) | 2006-02-16 | 2007-08-22 | Fujitsu Ltd. | Resist cover film-forming material, process for forming resist pattern, semiconductor device and process for manufacturing the same |
JP2007214279A (ja) * | 2006-02-08 | 2007-08-23 | Tokyo Electron Ltd | 塗布、現像装置、塗布、現像方法及びその方法を実施するためのコンピュータプログラム。 |
WO2008041476A1 (fr) * | 2006-09-29 | 2008-04-10 | Asahi Glass Company, Limited | Composition de formation d'un film de protection de résist et processus de formation de motifs de résist |
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JP2005060664A (ja) * | 2003-07-31 | 2005-03-10 | Asahi Glass Co Ltd | 含フッ素化合物、含フッ素ポリマーとその製造方法およびそれを含むレジスト組成物 |
WO2006011427A1 (ja) * | 2004-07-30 | 2006-02-02 | Asahi Glass Company, Limited | 含フッ素化合物、含フッ素ポリマー、レジスト組成物、およびレジスト保護膜組成物 |
US20090042148A1 (en) * | 2007-08-06 | 2009-02-12 | Munirathna Padmanaban | Photoresist Composition for Deep UV and Process Thereof |
WO2020040178A1 (ja) * | 2018-08-23 | 2020-02-27 | 東京エレクトロン株式会社 | 基板処理方法及び基板処理システム |
EP3689980A1 (en) * | 2019-01-31 | 2020-08-05 | 3M Innovative Properties Company | Fluoropolymer compositions |
JP2022151614A (ja) * | 2021-03-23 | 2022-10-07 | 信越化学工業株式会社 | ネガ型感光性樹脂組成物、パターン形成方法、硬化被膜形成方法、層間絶縁膜、表面保護膜、及び電子部品 |
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JP2007214279A (ja) * | 2006-02-08 | 2007-08-23 | Tokyo Electron Ltd | 塗布、現像装置、塗布、現像方法及びその方法を実施するためのコンピュータプログラム。 |
US9214363B2 (en) | 2006-02-08 | 2015-12-15 | Tokyo Electron Limited | Coating and developing apparatus, coating film forming method, and storage medium storing program for performing the method |
EP1821148A2 (en) | 2006-02-16 | 2007-08-22 | Fujitsu Ltd. | Resist cover film-forming material, process for forming resist pattern, semiconductor device and process for manufacturing the same |
EP1821148A3 (en) * | 2006-02-16 | 2008-10-29 | Fujitsu Ltd. | Resist cover film-forming material, process for forming resist pattern, semiconductor device and process for manufacturing the same |
US7608386B2 (en) | 2006-02-16 | 2009-10-27 | Fujitsu Limited | Resist cover film-forming material, process for forming resist pattern, semiconductor device and process for manufacturing the same |
JP2007219152A (ja) * | 2006-02-16 | 2007-08-30 | Fujitsu Ltd | レジストカバー膜形成材料、レジストパターンの形成方法、半導体装置及びその製造方法 |
WO2008041476A1 (fr) * | 2006-09-29 | 2008-04-10 | Asahi Glass Company, Limited | Composition de formation d'un film de protection de résist et processus de formation de motifs de résist |
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KR20070038533A (ko) | 2007-04-10 |
EP1772468A1 (en) | 2007-04-11 |
JPWO2006011427A1 (ja) | 2008-05-01 |
EP1772468A4 (en) | 2008-07-30 |
US7498393B2 (en) | 2009-03-03 |
TW200615287A (en) | 2006-05-16 |
US20070154844A1 (en) | 2007-07-05 |
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