WO2011077993A1 - 感放射線性組成物 - Google Patents
感放射線性組成物 Download PDFInfo
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- WO2011077993A1 WO2011077993A1 PCT/JP2010/072420 JP2010072420W WO2011077993A1 WO 2011077993 A1 WO2011077993 A1 WO 2011077993A1 JP 2010072420 W JP2010072420 W JP 2010072420W WO 2011077993 A1 WO2011077993 A1 WO 2011077993A1
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- 0 C*C(C(C)(C)C)(C1=CC=C**1)O* Chemical compound C*C(C(C)(C)C)(C1=CC=C**1)O* 0.000 description 5
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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
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/22—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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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- 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
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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
- C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
Definitions
- the present invention relates to a radiation-sensitive composition useful as a resist suitable for ultrafine processing using various types of radiation such as ultraviolet rays, far ultraviolet rays, X-rays or charged particle beams.
- the processing size in lithography has been miniaturized, but conventional visible light (wavelength 800 to 400 nm) or near.
- ultraviolet rays wavelength 400 to 300 nm
- Patent Document 1 discloses a combination of a resin protected with a t-butyl group or a t-butoxycarbonyl group and a radiation-sensitive acid generator.
- a combination of a silyl group protected resin and a radiation sensitive acid generator is disclosed.
- many reports have been made on chemically amplified resists such as a resist (Patent Document 3) containing a resin having an acetal group and a radiation-sensitive acid generator.
- an object of the present invention is to provide a radiation-sensitive composition that has a high scum margin and thus has a good scum margin and can provide a resist pattern having a good shape.
- the radiation-sensitive composition of the present invention includes a polymer (A1) containing a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and the formula (1):
- the polymer (A) containing the polymer (A2) which does not contain the repeating unit represented, and the radiation sensitive acid generator (B) are contained, It is characterized by the above-mentioned.
- R 1 represents a hydrogen atom, a methyl group, or a trifluoromethyl group
- R 2 represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a carbon number 1 to 12 linear or branched alkoxyl group or a group represented by the following formula (1-1)
- i and j each independently represents an integer of 0 to 3, i + j ⁇ Satisfy 5
- R ′ each independently represents a hydrogen atom or a methyl group
- R ′′ represents a linear or branched alkyl group having 1 to 8 carbon atoms or a cyclic alkyl group.
- R 3 represents a hydrogen atom or a methyl group
- R 4 is (i) a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof independently of each other, or Represents a linear or branched alkyl group having 1 to 4 carbon atoms, or (ii) includes any two R 4 bonded to each other, each containing a bonded carbon atom Represents a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, and the remaining R 4 is a linear or branched alkyl group having 1 to 4 carbon atoms, or a group having 4 to 20 carbon atoms Represents a monovalent alicyclic hydrocarbon group or a derivative thereof;
- the polymer (A2) is a repeating compound represented by at least one selected from the following formulas (3-1), (3-2), and (3-3): It is characterized by containing units.
- R 5 represents a hydrogen atom or a methyl group.
- R 6 represents a hydrogen atom, a straight chain having 1 to 4 carbon atoms or Represents a branched alkyl group, a linear or branched alkoxyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms, represented by the formula (3-2)
- R 7 represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms
- k represents an integer of 0 to 3
- L represents a single bond Or an alkylene group having 1 to 3 carbon atoms.
- the said polymer (A2) contains the repeating unit represented by following formula (4), It is characterized by the above-mentioned.
- R 8 represents a hydrogen atom or a methyl group
- R 9 represents a polycyclic alicyclic hydrocarbon group having 7 to 20 carbon atoms.
- the radiation sensitive acid generator (B) in the radiation sensitive composition of this invention is characterized by including a nonionic radiation sensitive acid generator.
- the nonionic radiation-sensitive acid generator is a sulfonyloxyimide compound.
- the nonionic radiation sensitive acid generator is a sulfonyldiazomethane compound.
- the radiation-sensitive acid generator (B) further includes an onium salt compound that generates benzenesulfonic acid which may be further substituted with a fluorine atom.
- the radiation-sensitive composition of the present invention is a polymer (A) containing the polymer (A1) and the polymer (A2), so that the content of the polymer (A2) is particularly 1 to 50% by mass. Therefore, in the lithography process of a substrate having a step, the development dissolution rate can be increased even in a region where the exposure amount is low. Therefore, a resist pattern having an excellent scum margin and a good shape can be obtained.
- a resin component for a radiation-sensitive composition having an excellent scum margin can be obtained even when used for forming a resist pattern for an ion implantation mask.
- the present invention is based on such knowledge.
- the polymer (A1) in the present invention is an alkali-insoluble or alkali-insoluble polymer containing the repeating unit represented by the above formula (1), and becomes alkali-soluble when the acid-dissociable group is dissociated. It is a polymer and constitutes the resin component of the present invention. In addition to the repeating unit represented by the above formula (1), a repeating unit containing an acid dissociable group can be included.
- alkali insoluble or hardly alkali soluble means that a resist pattern is formed from a resist film formed using a radiation-sensitive composition containing an acid-dissociable group-containing resin (polymer A1 or polymer A2).
- the initial film of the film It means that 50% or more of the thickness remains after development.
- Examples of the linear or branched alkyl group having 1 to 12 carbon atoms of R 2 in the above formula (1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, Examples include 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like.
- Examples of the straight-chain or branched alkoxyl group having 1 to 12 carbon atoms include, for example, methoxyl group, ethoxyl group, n-propoxyl group, i-propoxyl group, n-butoxyl group, 2-methylpropoxy group. Group, 1-methylpropoxyl group, t-butoxyl group and the like.
- R 2 is preferably a methyl group, an ethyl group, an n-butyl group, or a t-butyl group.
- the plurality of R 2 may be the same as or different from each other.
- j is an integer of 0 to 3, preferably 0 or 1.
- i is an integer of 1 to 3, preferably 1 or 2.
- R ′′ represents a linear or branched alkyl group having 1 to 8 carbon atoms or a cyclic alkyl group.
- Examples of the linear or branched alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, and a 1-methyl group.
- Examples thereof include a group consisting of an alicyclic ring derived from a propyl group, t-butyl group, norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane and cyclohexane, and a group obtained by substituting these with an alkyl group.
- the repeating unit having an acid dissociable group that can be contained in the polymer (A1) is, for example, the acidic functional group in an alkali-soluble polymer having one or more acidic functional groups such as a phenolic hydroxyl group and a carboxyl group.
- the hydrogen atom is substituted with one or more acid-dissociable groups capable of dissociating in the presence of an acid, and examples thereof include a repeating unit capable of forming an alkali-insoluble or alkali-insoluble polymer. .
- a preferred acid dissociable group-containing polymer (A1) for example, a repeating unit represented by the following formula (5) (hereinafter referred to as “repeating unit (5)”) and a following formula (6) ) (Hereinafter referred to as “repeating unit (6)”) and / or a repeating unit represented by the following formula (7) (hereinafter referred to as “repeating unit (7)”).
- a polymer hereinafter referred to as “polymer (A1-a)”).
- R 10 represents a hydrogen atom or a methyl group
- R 11 represents a monovalent acid dissociable group
- l represents 1 to 1 It is an integer of 3
- R 12 represents a monovalent acid dissociable group.
- Examples of the monovalent acid dissociable group of R 11 in the formula (6) and R 12 in the formula (7) include, for example, a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a triorganosilyl group, a triorganosilyl group, Examples thereof include an organogermyl group, an alkoxycarbonyl group, an acyl group, and a monovalent cyclic acid dissociable group.
- t-butyl group benzyl group, 1-methoxyethyl group, 1-ethoxyethyl group, trimethylsilyl group, t-butoxycarbonyl group, t-butoxycarbonylmethyl group, tetrahydrofuranyl Group, tetrahydropyranyl group, tetrahydrothiofuranyl group, tetrahydrothiopyranyl group and the like are preferable.
- the preferred repeating unit (5) in the present invention includes a repeating unit in which a polymerizable unsaturated bond of 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene is cleaved.
- the repeating unit (5) may be present alone or in combination of two or more.
- the preferred repeating unit (6) in the present invention is, for example, 4-t-butoxystyrene, 4- (2-ethyl-2-propoxy) styrene, 4- (1-ethoxyethoxy) styrene, t-butoxycarbonyl.
- Examples thereof include a repeating unit in which a polymerizable unsaturated bond is cleaved, such as styrene and t-butoxycarbonylmethylenestyrene.
- the repeating unit (6) may be present alone or in combination of two or more.
- the repeating unit (7) in the present invention includes t-butyl (meth) acrylate, 1-methyladamantyl (meth) acrylate, 1-ethyladamantyl acrylate, 1-methylcyclopentyl (meth) acrylate and ( Both 1-ethylcyclopentyl (meth) acrylate and 2,5-dimethylhexane-2,5-diacrylate are preferred.
- the repeating unit (7) may be present alone or in combination of two or more.
- the polymer (A1) can further have a repeating unit other than the repeating unit (5) to the repeating unit (7) (hereinafter referred to as “other repeating unit”).
- Other repeating units include, for example, vinyl aromatic compounds such as styrene, (meth) acrylic acid esters, carboxyalkyl esters of unsaturated carboxylic acids, unsaturated amide compounds, unsaturated imide compounds, nitrogen-containing vinyl compounds, etc. And a unit in which the polymerizable unsaturated bond is cleaved.
- other repeating units may be present alone or in combination of two or more.
- Particularly preferred polymers (A1) in the present invention include, for example, 4-hydroxystyrene / 4-t-butoxystyrene copolymer, 4-hydroxystyrene / 4-t-butoxystyrene / 1-methylcyclopentyl acrylate copolymer.
- the acid dissociable group introduction rate (the acid relative to the total number of unprotected acidic functional groups and acid dissociable groups in the acid dissociable group-containing polymer (A1))
- the ratio of the number of dissociable groups cannot be defined unconditionally depending on the type of the acid dissociable group and the alkali-soluble resin into which the group is introduced, but is preferably 10 to 100%, more preferably 15 to 100%. .
- the content of the repeating unit (5) is preferably 50 to 80 mol%, more preferably 65 to 75 mol%, and the content of the repeating unit (6) is preferably 10 to 40 mol%, more preferably 20 to 35 mol%, and the content of the repeating unit (7) is preferably 2 to 40 mol%, more preferably 10 to 30 mol%.
- the rate is usually 25 mol% or less, preferably 10 mol% or less.
- the resolution tends to decrease, and when it exceeds 40 mol%, the adhesion of the resist pattern to the substrate tends to decrease.
- the content of the repeating unit (7) is less than 2 mol%, the resolution tends to decrease.
- the content exceeds 40%, the dry etching resistance may be insufficient.
- the other repeating unit exceeds 25 mol%, the resolution tends to decrease.
- the polystyrene-reduced weight molecular weight (hereinafter referred to as “Mw”) of the acid dissociable group-containing polymer (A1) measured by gel permeation chromatography (GPC) is preferably 1,000 to 150,000, more preferably 3,000 to 100,000. Further, the ratio (Mw / Mn) of Mw of the acid dissociable group-containing polymer (A1) and polystyrene-reduced number molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC) is usually 1 to 10, preferably 1 to 5.
- the acid dissociable group-containing polymer (A1) was polymerized, for example, with a polymerizable unsaturated monomer corresponding to the repeating unit (5) together with a polymerizable unsaturated monomer that optionally gave another repeating unit. Thereafter, it can be produced by introducing one or more monovalent acid dissociable groups (R 11 ) into the phenolic hydroxyl group, and the polymerizable unsaturated monomer corresponding to the repeating unit (5) It can manufacture by copolymerizing the polymerizable unsaturated monomer corresponding to a repeating unit (6) with the polymerizable unsaturated monomer which gives another repeating unit depending on the case.
- an acid dissociable group containing polymer (A1) can be used individually or in mixture of 2 or more types.
- the polymer (A2) in the present invention is an alkali-insoluble or hardly alkali-soluble polymer containing the repeating unit represented by the above formula (2) and not containing the repeating unit represented by the above formula (1).
- the acid-dissociable group is a polymer that becomes alkali-soluble when dissociated, and constitutes the resin component of the present invention.
- R 4 in formula (2) a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms and a group formed by bonding any two R 4 to each other , Norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane, a group composed of an alicyclic ring derived from cyclohexane, or a group obtained by substituting these with an alkyl group.
- a group composed of the above alicyclic ring or an alkyl substituent thereof may be a hydroxyl group or a group having 1 to 4 carbon atoms.
- examples thereof include a group substituted with one or more substituents such as a hydroxyalkyl group, an alkoxyl group having 1 to 4 carbon atoms, a cyano group, and a cyanoalkyl group having 2 to 5 carbon atoms.
- substituents such as a hydroxyalkyl group, an alkoxyl group having 1 to 4 carbon atoms, a cyano group, and a cyanoalkyl group having 2 to 5 carbon atoms.
- a hydroxyl group, a carboxyl group, a hydroxymethyl group, a cyano group, and a group substituted with a cyanomethyl group are preferable.
- linear or branched alkyl group having 1 to 4 carbon atoms specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group , 1-methylpropyl group, t-butyl group and the like.
- a methyl group and an ethyl group are preferable.
- R 13 independently represents a linear or branched alkyl group having 1 to 4 carbon atoms.
- m represents 0 or 1.
- examples of the linear or branched alkyl group having 1 to 4 carbon atoms represented by R 13 include a methyl group, an ethyl group, n Examples include -propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like. Among these, a methyl group and an ethyl group are preferable.
- repeating units in the polymer (A2) in addition to the (meth) acrylic acid ester described above, repeating units of the above formulas (3-1) to (3-3) can be included.
- examples of the linear or branched alkyl group having 1 to 4 carbon atoms represented by R 6 include a methyl group, an ethyl group, an n-propyl group, and i-propyl. Group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like. Among these, a methyl group and an ethyl group are preferable.
- examples of the linear or branched alkoxyl group having 1 to 4 carbon atoms represented by R 6 include methoxyl group, ethoxyl group, n-propoxyl group, i- Examples include propoxyl group, n-butoxyl group, 2-methylpropoxyl group, 1-methylpropoxyl group, t-butoxyl group and the like.
- examples of the linear or branched fluorinated alkyl group having 1 to 4 carbon atoms represented by R 6 specifically, some or all of the hydrogen atoms of the above alkyl group And a group substituted with a fluorine atom.
- examples of the linear or branched alkyl group having 1 to 4 carbon atoms represented by R 7 include methyl, ethyl, n-propyl, i-propyl. Group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like. Among these, a methyl group and an ethyl group are preferable.
- examples of the alkylene group having 1 to 3 carbon atoms represented by L include a methylene group, an ethylene group, an n-propylene group, and an i-propylene group. .
- the polymer (A2) can have a repeating unit represented by the above formula (4).
- R 8 is preferably a methyl group
- the polycyclic alicyclic hydrocarbon group having 7 to 20 carbon atoms represented by R 9 is represented by the following formulas (5-1) to (5-6). ) Is preferred.
- the content of the repeating unit (2) is preferably 20 to 80 mol%, more preferably 30 to 60 mol%, and is represented by the formula (3-1), the formula (3-2) and
- the content of the repeating unit represented by at least one selected from the formula (3-3) is preferably 20 to 70 mol%, more preferably 30 to 60 mol%, and the content of the repeating unit (4). Is preferably 0 to 30 mol%, more preferably 0 to 20 mol%. In this case, if the content of the repeating unit (2) is less than 20 mol%, the resolution tends to be lowered, whereas if it exceeds 80 mol%, the developability tends to be lowered.
- the content of the repeating unit (3-1) or the like is less than 20 mol%, the developability tends to be lowered, while if it exceeds 70 mol%, the scum reducing effect tends to be lowered.
- the content rate of a repeating unit (4) exceeds 30 mol%, there exists a possibility that resolution may become inadequate.
- the resin component of the present invention is a polymer (A) containing the polymer (A1) and the polymer (A2).
- the mixing ratio of the polymer (A) is such that the polymer (A2) is contained in an amount of 1 to 50% by mass, preferably 3 to 30% by mass, when the total amount of the polymer (A) is 100% by mass. If the polymer (A2) is less than 1% by mass, the effect of reducing scum is low, and if it exceeds 50% by mass, the compatibility with the polymer (A1) decreases and the roughness tends to deteriorate.
- the radiation sensitive acid generator (B) (hereinafter referred to as acid generator (B)) is a component that generates an acid upon exposure.
- a nonionic radiation sensitive acid generator is preferred.
- the sulfonyloxyimide compound represented by following formula (8) can be mentioned, for example.
- R 14 represents an alkylene group, an arylene group, an alkoxylene group, a cycloalkylene group, a divalent group such as a cycloalkylene group containing a cyclic skeleton having an unsaturated bond
- R 15 is a halogen atom.
- a sulfonyloxyimide compound can be used individually or in mixture of 2 or more types.
- sulfonyloxyimide compound examples include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) succinimide.
- each R 16 is independently an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group, a halogen-substituted alkyl group, a halogen-substituted aryl group, etc. Represents a monovalent group.
- sulfonyldiazomethane compound examples include bis (trifluoromethanesulfonyl) diazomethane, bis (cyclohexanesulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-toluenesulfonyl) diazomethane, bis (2,4-dimethylbenzenesulfonyl).
- Diazomethane bis (4-t-butylphenylsulfonyl) diazomethane, bis (4-chlorobenzenesulfonyl) diazomethane, methylsulfonyl, 4-toluenesulfonyldiazomethane, cyclohexanesulfonyl, 4-toluenesulfonyldiazomethane, cyclohexanesulfonyl, 1,1-dimethylethane Sulfonyldiazomethane, bis (1,1-dimethylethanesulfonyl) diazomethane, bis (1-methylethanesulfonyl) di Zomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl) diazomethane, bis (1,4-dioxaspiro [4.5] decan-7-sul
- An onium salt compound can be used as the acid generator (B).
- Specific examples of the onium salt compound include compounds represented by the following formula (10) or (11).
- R 17 and R 18 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, or an optionally substituted carbon number 6 Or an aryl group of ⁇ 18, or R 17 and R 18 are bonded to each other to form a cyclic structure together with an iodine atom in the formula.
- R 19 , R 20 and R 21 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, or may be substituted
- a good aryl group having 6 to 18 carbon atoms, or any two of R 19 , R 20 , and R 21 are bonded to each other to form a cyclic structure together with the sulfur atom in the formula,
- One is a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, or an aryl group having 6 to 18 carbon atoms which may be substituted.
- X ⁇ represents R—SO 3 — or R—COOH —
- R— represents an alkyl group or aromatic which may be substituted with a fluorine atom, a hydroxyl group, an alkoxyl group, or a carboxyl group.
- Preferred R—SO 3 — includes trifluoromethanesulfonate, nonafluoro-n-butanesulfonate, benzenesulfonate, 10-camphorsulfonate, 2-trifluoromethylbenzenesulfonate, 4-trifluoromethylbenzenesulfonate, and 2,4-difluorobenzene.
- Preferred R-COOH in - - X used in equation (10) and (11) include a group represented by the following formula (X-1) ⁇ formula (X-8).
- each R 22 is independently a linear or branched monovalent aliphatic hydrocarbon group, cycloalkyl group, aryl group, aralkyl group, or other monovalent organic having a hetero atom.
- V and W each independently represent an aryl group, a hydrogen atom, a linear or branched monovalent aliphatic hydrocarbon group or another monovalent organic group having a hetero atom, and At least one of V and W is an aryl group, or V and W are connected to each other to form a carbon monocyclic structure or a carbon polycyclic structure having at least one unsaturated bond; W are connected to each other to form a group represented by the following formula (13).
- V ′ and W ′ are independent from each other, and a plurality of V ′ and W ′ may be the same or different, and each represents a hydrogen atom, a halogen atom, a linear or branched alkyl group , A cycloalkyl group, an aryl group or an aralkyl group, or V ′ and W ′ bonded to the same or different carbon atoms are connected to each other to form a carbon monocyclic structure, and r is 2 to 10 Is an integer.
- Examples of the oxime sulfonate compound include compounds represented by the following formula (13-1) or formula (13-2).
- each R 23 and each R 24 independently represent a monovalent organic group.
- These other acid generators can be used alone or in admixture of two or more.
- the amount of the acid generator (B) used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight per 100 parts by weight of the acid dissociable group-containing resin (A). is there.
- the amount of the acid generator (B) used is less than 0.1 parts by mass, the sensitivity and developability tend to decrease.
- the amount exceeds 20 parts by mass the transparency to radiation, pattern shape, and heat resistance Etc. tend to decrease.
- the use ratio of the acid generator other than the sulfonyloxyimide compound, the sulfonyldiazomethane compound, and the onium salt compound that generates benzenesulfonic acid optionally substituted with a fluorine atom is based on the total amount of the acid generator (B). Usually, it is 30% by mass or less, preferably 10% by mass or less. In this case, if the use ratio of the other acid generator exceeds 30% by mass, the intended effect of the present invention may be impaired.
- the radiation-sensitive composition of the present invention can contain an acid diffusion controller and a surfactant.
- Acid diffusion control agent is a component having an action of controlling a diffusion phenomenon in the resist film of an acid generated from the acid generator (B) by exposure and suppressing an undesirable chemical reaction in a non-exposed region.
- the storage stability of the resulting radiation-sensitive composition is improved.
- the resolution of the formed resist film is further improved, and changes in the line width of the resist pattern due to fluctuations in the holding time (PED) after exposure until heat treatment can be suppressed, thereby improving process stability.
- An extremely excellent radiation sensitive composition is obtained.
- Examples of the acid diffusion control agent include nitrogen-containing organic compounds.
- Examples of the nitrogen-containing organic compound include a compound represented by the following formula (14) (hereinafter referred to as “nitrogen-containing compound (i)”), a nitrogen atom of 2 in the same molecule represented by the following formula (15).
- a compound having a number hereinafter referred to as “nitrogen-containing compound (ii)”
- a polyamino compound or polymer having three or more nitrogen atoms hereinafter collectively referred to as “nitrogen-containing compound (iii)”
- Examples thereof include amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds represented by 16).
- R 25 are independently of each other a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, or a substituted It is also a good aralkyl group.
- the nitrogen-containing compound (i) include substituted alkylamines such as di (cyclo) alkylamines, tri (cyclo) alkylamines and trialcoholamines, and aromatic amines such as anilines.
- R 26 are independently of each other a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, or a substituted
- L ′ represents a single bond or an alkylene group having 1 to 6 carbon atoms, an ether group, a carbonyl group or an alkoxycarbonyl group.
- the nitrogen-containing compound (iii) include triazines, polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide polymer, and the like.
- R 27 are independently of each other a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, or a substituted R 27 may be bonded to each other to form a heterocyclic structure.
- R 28 represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group which may be substituted, or an aralkyl group which may be substituted.
- urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea.
- Etc. examples of the nitrogen-containing heterocyclic compound include imidazoles, pyridines, piperazines, piperidines, triazines, and morpholines, as well as pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, 1,4-diazabicyclo [2. 2.2]
- a preferred example is octane.
- the acid diffusion control agents can be used alone or in admixture of two or more.
- the compounding amount of the acid diffusion control agent is usually 15 parts by mass or less, preferably 0.001 to 10 parts by mass, more preferably 0.005 to 5 parts by mass per 100 parts by mass of the acid dissociable group-containing resin (A). It is. In this case, when the compounding amount of the acid diffusion controller exceeds 15 parts by mass, the sensitivity as a resist and the developability of the exposed part tend to be lowered. In addition, if the compounding quantity of an acid diffusion control agent is less than 0.001 mass part, there exists a possibility that the pattern shape and dimension fidelity as a resist may fall depending on process conditions.
- a surfactant exhibiting an effect of improving the coating property and striation of the composition, the developability as a resist, and the like can be blended.
- surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenol ether, polyoxyethylene n-nonylphenol ether, polyethylene glycol dilaurate, polyethylene Glycol distearate and the like can be mentioned, and as commercial products, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), Megafax F171, F173 (Dainippon Ink) Chemical Industry Co., Ltd.), Florard FC430, FC431 (Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC 03 (manufactured by Asa
- the surfactants can be used alone or in admixture of two or more.
- the compounding amount of the surfactant is usually 2 parts by mass or less per 100 parts by mass of the acid dissociable group-containing resin (A).
- the positive-type radiation-sensitive composition of the present invention is usually uniform in the solvent so that the total solid content is usually 0.1 to 50% by mass, preferably 1 to 40% by mass when used. Then, it is prepared as a composition solution by, for example, filtering with a filter having a pore size of about 0.2 ⁇ m.
- the solvent used for preparing the composition solution include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate and the like.
- Monoalkyl ether acetates propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether , Propylene glycol di-n-propyl ether, propylene glycol Propylene glycol dialkyl ethers such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate Ether acetates;
- Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate; n-amyl formate, i-amyl formate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate Aliphatic carboxylic acid esters such as i-butyl acetate, n-amyl acetate, i-amyl acetate, i-propyl propionate, n-butyl propionate and i-butyl propionate; ethyl hydroxyacetate, 2-hydroxy- Ethyl 2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate
- Synthesis example 1 Compound 103g (70 mol%) represented by the following formula (L-1), compound 40g (25 mol%) represented by the following formula (L-2), compound represented by the following formula (L-3) 5 g (5 mol%), 6 g of azobisisobutyronitrile (AIBN) and 1 g of t-dodecyl mercaptan were dissolved in 160 g of propylene glycol monomethyl ether, and the reaction temperature was maintained at 70 ° C. under a nitrogen atmosphere. Polymerized for hours.
- AIBN azobisisobutyronitrile
- the reaction solution was dropped into a large amount of n-hexane to coagulate and purify the resulting polymer.
- 150 g of propylene glycol monomethyl ether was added to the purified polymer, and then 300 g of methanol, 80 g of triethylamine and 15 g of water were further added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point.
- the solvent and triethylamine were distilled off under reduced pressure, and the resulting polymer was dissolved in acetone, then dripped into a large amount of water to solidify, and the resulting white powder was filtered and filtered under reduced pressure at 50 ° C. overnight. Dried.
- Synthesis example 2 174 g (75 mol%) of the compound represented by the above formula (L-1), 55 g (22 mol%) of the compound represented by the above formula (L-2), and a compound represented by the following formula (L-4) 11 g (3 mol%), 14 g of AIBN and 11 g of t-dodecyl mercaptan were dissolved in 240 g of propylene glycol monomethyl ether, and then polymerized for 16 hours while maintaining the reaction temperature at 70 ° C. in a nitrogen atmosphere. After the polymerization, the reaction solution was dropped into a large amount of n-hexane to coagulate and purify the produced polymer, and dried at 50 ° C. under reduced pressure for 3 hours.
- Synthesis example 3 25 g of a p-hydroxystyrene / pt-butoxystyrene copolymer having a copolymer molar ratio of 90:10 was dissolved in 100 g of n-butyl acetate and bubbled with nitrogen gas for 30 minutes. 3 g was added, 1 g of p-toluenesulfonic acid pyridinium salt was added as a catalyst, and the mixture was reacted at room temperature for 12 hours. Thereafter, the reaction solution was dropped into a 1% by mass aqueous ammonia solution to solidify the polymer, filtered, and dried overnight at 50 ° C. under reduced pressure.
- Synthesis example 4 150 g (65 mol%) of the compound represented by the above formula (L-1), 25 g (10 mol%) of the compound represented by the above formula (L-2), and a compound represented by the following formula (L-5) 65 g (25 mol%), 14 g of AIBN and 11 g of t-dodecyl mercaptan were dissolved in 240 g of propylene glycol monomethyl ether, and then polymerization was performed for 16 hours while maintaining the reaction temperature at 70 ° C. in a nitrogen atmosphere. After the polymerization, the reaction solution was dropped into a large amount of n-hexane to coagulate and purify the produced polymer, and dried at 50 ° C. under reduced pressure for 3 hours.
- Synthesis example 5 54 g (50 mol%) of the compound represented by the following formula (L-6), 11 g (10 mol%) of the compound represented by the following formula (L-7), and the above formula (L-5) 35 g (40 mol%) of the compound was dissolved in 200 g of 2-butanone, and 5.58 g of AIBN was further added to prepare a monomer solution.
- a 1000 mL three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes, then heated to 80 ° C. with stirring, and the prepared monomer solution was added dropwise over 3 hours using a dropping funnel. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time.
- the polymer solution was cooled to 30 ° C. or less by water cooling, and then poured into 2000 g of methanol, and the precipitated white powder was filtered off.
- the filtered white powder was washed twice on the slurry with 400 g of methanol, filtered, and dried at 50 ° C. for 17 hours to obtain a white powder polymer (74 g, yield 74%).
- Mw of the obtained polymer was 6,900, and Mw / Mn was 1.70.
- Synthesis Example 6 54 g (50 mol%) of the compound represented by the above formula (L-6), 11 g (10 mol%) of the compound represented by the above formula (L-7), and the following formula (L-8) 35 g (40 mol%) of the compound was dissolved in 200 g of 2-butanone, and 5.58 g of AIBN was further added to prepare a monomer solution. A 1000 mL three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes, then heated to 80 ° C. with stirring, and the prepared monomer solution was added dropwise over 3 hours using a dropping funnel. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time.
- the polymer solution was cooled to 30 ° C. or less by water cooling, and then poured into 2000 g of methanol, and the precipitated white powder was filtered off.
- the filtered white powder was washed twice on the slurry with 400 g of methanol, filtered, and dried at 50 ° C. for 17 hours to obtain a white powder polymer (74 g, yield 74%).
- Mw of the obtained polymer was 8,000 and Mw / Mn was 1.70.
- Synthesis example 7 instead of the compound represented by the above formula (L-7), 39 g (37 mol%) of the compound represented by the following formula (L-9) was used, and represented by the above formula (L-6). A polymer was obtained in the same manner as in Synthesis Example 5, except that 50 g (50 mol%) of the compound and 11 g (13 mol%) of the compound represented by the above formula (L-5) were used. (78 g, 78% yield). Mw of the obtained polymer was 5,200, and Mw / Mn was 1.62.
- Synthesis example 8 The compound represented by the above formula (L-6) was obtained by using 10 g (10 mol%) of the compound represented by the following formula (L-10) instead of the compound represented by the above formula (L-7). A polymer was obtained in the same manner as in Synthesis Example 5 except that 55 g (50 mol%) was used and 36 g (40 mol%) of the compound represented by the above formula (L-5) was used ( 71 g, 71% yield). Mw of the obtained polymer was 8,100, Mw / Mn was 1.69, and the residual ratio of the low molecular weight component was 0.04%.
- each resist was evaluated in the following manner.
- sensitivity As shown in FIG. 1, a wafer was prepared on a silicon substrate 1 having a height difference of 100 nm, a line width of 90 nm, and a polysilicon step 2 having a space of 180 nm. As shown in FIG. 2, the optimum exposure amount for forming a 180 nm line-and-space pattern (1L1S) of the resist pattern 3 perpendicular to the polysilicon step 2 on this wafer has a one-to-one line width. The exposure amount was set, and this optimum exposure amount was set as the sensitivity.
- Scum margin An enlarged view of the resist pattern when exposed at the optimum exposure amount shown in FIG. 2 is shown in FIG.
- the resist pattern of the scum 4 and the width t of the scum end generated in the exposed portion near the portion where the resist pattern 3 and the step 2 intersect each other were measured. shape: If the resist pattern is observed with a CD (Critical Dimension) (scanning electron microscope), and the white edge (edge chipping) of the line pattern of the resist pattern is 5 nm or less when exposed at the optimum exposure amount, it is good. When it exceeded, it was defined as bad.
- CD Cosmetic Dimension
- each resist film was exposed using a KrF excimer laser irradiation apparatus NSR-S203B (trade name, manufactured by Nikon Corporation) with a KrF excimer laser (wavelength 248 nm) through a mask pattern while changing the exposure amount.
- PEB was performed at 90 ° C. for 90 seconds.
- a 2.38 mass% tetramethylammonium hydroxide aqueous solution was used as a developing solution, developed at 23 ° C. for 60 seconds, washed with water for 30 seconds, and dried to form a resist pattern.
- the resist pattern was observed using a CD-scanning electron microscope S-9220 (trade name, manufactured by Hitachi High-Technologies Corporation). Table 2 shows the evaluation results of the examples and comparative examples.
- each component other than the resin (A) is as follows.
- B-6 triphenylsulfonium nonafluorobutanesulfonate diffusion
- C-1 2-phenylbenzimidazole solvent
- D-1 Ethyl lactate
- D-2 Propylene glycol monomethyl ether acetate
- the radiation-sensitive composition of the present invention has an excellent scum margin and a resist pattern having a good shape can be obtained, it can be suitably used as a lithography material using a KrF excimer laser as a light source.
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Abstract
Description
そして、エキシマレーザー等の遠紫外線に適したレジストとして、放射線の照射(以下、「露光」ともいう。)により酸を生成する感放射線性酸発生剤を使用し、その酸の触媒作用によりレジストの感度を向上させた「化学増幅型レジスト」が使用されている。
このような化学増幅型レジストとしては、例えば、特許文献1に、t-ブチル基あるいはt-ブトキシカルボニル基で保護された樹脂と感放射線性酸発生剤との組合せが、また特許文献2には、シリル基で保護された樹脂と感放射線性酸発生剤との組合せが、それぞれ開示されている。またその他にも、アセタール基を有する樹脂と感放射線性酸発生剤とを含有するレジスト(特許文献3)等、化学増幅型レジストに関しては多くの報告がなされている。
式(2)において、R3は、水素原子またはメチル基を表し、R4は、(i)相互に独立に、炭素数4~20の1価の脂環式炭化水素基もしくはその誘導体、または炭素数1~4の直鎖状もしくは分岐状のアルキル基を表すか、または、(ii)いずれか二つのR4が相互に結合して形成される、それぞれが結合している炭素原子を含む炭素数4~20の2価の脂環式炭化水素基またはその誘導体を表し、残りのR4が、炭素数1~4の直鎖状もしくは分岐状のアルキル基、または炭素数4~20の1価の脂環式炭化水素基もしくはその誘導体を表す。
また、本発明の感放射線性組成物における感放射線性酸発生剤(B)は、非イオン性感放射線性酸発生剤を含むことを特徴とする。
特に上記非イオン性感放射線性酸発生剤が、スルホニルオキシイミド化合物であることを特徴とする。また、上記非イオン性感放射線性酸発生剤が、スルホニルジアゾメタン化合物であることを特徴とする。また、上記感放射線性酸発生剤(B)が、更にフッ素原子で置換されていてもよいベンゼンスルホン酸を発生するオニウム塩化合物を含むことを特徴とする。
本発明における重合体(A1)は、上記式(1)で表される繰り返し単位を含むアルカリ不溶性またはアルカリ難溶性の重合体であって、該酸解離性基が解離することによりアルカリ可溶性となる重合体であり、本発明の樹脂成分を構成する。上記式(1)で表される繰り返し単位に加えて、酸解離性基を含む繰り返し単位を含ませることができる。
本発明において、「アルカリ不溶性またはアルカリ難溶性」とは、酸解離性基含有樹脂(重合体A1または重合体A2)を含有する感放射線性組成物を用いて形成されるレジスト被膜からレジストパターンを形成する際に採用されるアルカリ現像条件下で、当該レジスト被膜の代わりに酸解離性基含有樹脂(重合体A1または重合体A2)のみを用いた被膜を現像した場合に、当該被膜の初期膜厚の50%以上が現像後に残存する性質を意味する。
また、同炭素数1~12の直鎖状もしくは分岐状のアルコキシル基としては、例えば、メトキシル基、エトキシル基、n-プロポキシル基、i-プロポキシル基、n-ブトキシル基、2-メチルプロポキシル基、1-メチルプロポキシル基、t-ブトキシル基等が挙げられる。
これらの中で、R2としてはメチル基、エチル基、n-ブチル基、t-ブチル基が好ましい。
また、R2が複数存在する場合には、その複数のR2は、相互に同一であっても異なっていてもよい。
jは0~3の整数であり、好ましくは0または1である。iは1~3の整数であり、好ましくは1または2である。
炭素数1~8の直鎖状もしくは分岐状のアルキル基としては、例えば、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、2-メチルプロピル基、1-メチルプロピル基、t-ブチル基、ノルボルナン、トリシクロデカン、テトラシクロドデカン、アダマンタン、シクロペンタン、シクロヘキサンに由来する脂環族環からなる基や、これらをアルキル基で置換した基等が挙げられる。
本発明において、好ましい酸解離性基含有重合体(A1)としては、例えば、下記式(5)で表される繰り返し単位(以下、「繰り返し単位(5)」という。)と、下記式(6)で表される繰り返し単位(以下、「繰り返し単位(6)」という。)および/または下記式(7)で表される繰り返し単位(以下、「繰り返し単位(7)」という。)とを有する重合体(以下、「重合体(A1-a)」という。)を挙げることができる。
これらの1価の酸解離性基のうち、t-ブチル基、ベンジル基、1-メトキシエチル基、1-エトキシエチル基、トリメチルシリル基、t-ブトキシカルボニル基、t-ブトキシカルボニルメチル基、テトラヒドロフラニル基、テトラヒドロピラニル基、テトラヒドロチオフラニル基、テトラヒドロチオピラニル基等が好ましい。
重合体(A1-a)において、繰り返し単位(5)は、単独でまたは2種以上が存在することができる。
また、本発明における好ましい繰り返し単位(6)としては、例えば、4-t-ブトキシスチレン、4-(2-エチル-2-プロポキシ)スチレン、4-(1-エトキシエトキシ)スチレン、t-ブトキシカルボニルスチレン、t-ブトキシカルボニルメチレンスチレン、等の重合性不飽和結合が開裂した繰り返し単位を挙げることができる。
重合体(A1-a)において、繰り返し単位(6)は、単独でまたは2種以上が存在することができる。
また、本発明における繰り返し単位(7)としては、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸1-メチルアダマンチル、アクリル酸1-エチルアダマンチル、(メタ)アクリル酸1-メチルシクロペンチルおよび(メタ)アクリル酸1-エチルシクロペンチル、2,5-ジメチルヘキサン-2,5-ジアクリレートがいずれも好ましい。
重合体(A1-a)において、繰り返し単位(7)は、単独でまたは2種以上が存在することができる。
他の繰り返し単位としては、例えば、スチレンなどのビニル芳香族化合物、(メタ)アクリル酸エステル類、不飽和カルボン酸のカルボキシアルキルエステル類、不飽和アミド化合物、不飽和イミド化合物、含窒素ビニル化合物等の重合性不飽和結合が開裂した単位を挙げることができる。
重合体(A1)において、他の繰り返し単位は、単独でまたは2種以上が存在することができる。
また、酸解離性基含有重合体(A1)のMwとゲルパーミエーションクロマトグラフィー(GPC)で測定したポリスチレン換算数分子量(以下、「Mn」という。)との比(Mw/Mn)は、通常、1~10、好ましくは1~5である。
本発明において、酸解離性基含有重合体(A1)は、単独でまたは2種以上を混合して使用することができる。
本発明における重合体(A2)は、上記式(2)で表される繰り返し単位を含み、上記式(1)で表される繰り返し単位を含まない、アルカリ不溶性またはアルカリ難溶性の重合体であって、該酸解離性基が解離することによりアルカリ可溶性となる重合体であり、本発明の樹脂成分を構成する。
式(2)において、R4として表される基のうち、炭素数4~20の1価の脂環式炭化水素基、およびいずれか二つのR4が相互に結合して形成される基として、ノルボルナン、トリシクロデカン、テトラシクロドデカン、アダマンタン、シクロペンタン、シクロヘキサンに由来する脂環族環からなる基や、これらをアルキル基で置換した基が好ましく挙げられる。
また、炭素数4~20の1価の脂環式炭化水素基の誘導体として、具体的には、上記脂環族環からなる基や、これらのアルキル置換基を水酸基、炭素数1~4のヒドロキシアルキル基、炭素数1~4のアルコキシル基、シアノ基、炭素数2~5のシアノアルキル基等の置換基の1種以上で置換した基を挙げることができる。これらの中でも、水酸基、カルボキシル基、ヒドロキシメチル基、シアノ基、シアノメチル基で置換した基が好ましい。
更に、炭素数1~4の直鎖状または分岐状のアルキル基として、具体的には、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、2-メチルプロピル基、1-メチルプロピル基、t-ブチル基等を挙げることができる。これらの中でも、メチル基、エチル基が好ましい。
式(2-1)~式(2-5)において、R13として表される炭素数1~4の直鎖状または分岐状のアルキル基として、具体的には、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、2-メチルプロピル基、1-メチルプロピル基、t-ブチル基等を挙げることができる。これらの中でも、メチル基、エチル基が好ましい。
式(3-1)において、R6として表される炭素数1~4の直鎖状もしくは分岐状のアルキル基として、具体的には、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、2-メチルプロピル基、1-メチルプロピル基、t-ブチル基等を挙げることができる。これらの中でも、メチル基、エチル基が好ましい。
式(3-1)において、R6として表される炭素数1~4の直鎖状もしくは分岐状のアルコキシル基として、具体的には、メトキシル基、エトキシル基、n-プロポキシル基、i-プロポキシル基、n-ブトキシル基、2-メチルプロポキシル基、1-メチルプロポキシル基、t-ブトキシル基等が挙げられる。
式(3-1)において、R6として表される炭素数1~4の直鎖状もしくは分岐状のフッ素化アルキル基として、具体的には、上記アルキル基の水素原子の一部または全部をフッ素原子で置き換えた基が挙げられる。
式(3-2)において、R7として表される炭素数1~4の直鎖状もしくは分岐状のアルキル基として、具体的には、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、2-メチルプロピル基、1-メチルプロピル基、t-ブチル基等を挙げることができる。これらの中でも、メチル基、エチル基が好ましい。
式(3-3)において、Lとして表される炭素数1~3のアルキレン基として、メチレン基、エチレン基、n-プロピレン基、i-プロピレン基を挙げることができる。
。
式(4)において、R8はメチル基が好ましく、R9として表される炭素数7~20の多環型脂環式炭化水素基は、下記式(5-1)~式(5-6)が好ましい。
感放射線性酸発生剤(B)(以下、酸発生剤(B)という)は、露光により酸を発生する成分である。酸発生剤(B)としては、非イオン性感放射線性酸発生剤が好ましい。非イオン性感放射線性酸発生剤としては、例えば、下記式(8)で表されるスルホニルオキシイミド化合物を挙げることができる。
オニウム塩化合物の具体例としては、下記式(10)または(11)で表される化合物を挙げることができる。
式(11)中、R19、R20、及びR21は、相互に独立に、置換されていてもよい炭素数1~10の直鎖状もしくは分岐状のアルキル基、または置換されていてもよい炭素数6~18のアリール基であるか、あるいは、R19、R20、およびR21のいずれか2つが相互に結合して式中のイオウ原子とともに環状構造を形成しており、残りの1つが置換されていてもよい炭素数1~10の直鎖状もしくは分岐状のアルキル基、または置換されていてもよい炭素数6~18のアリール基である。
好ましいR-SO3 -としては、トリフルオロメタンスルホネート、ノナフルオロ-n-ブタンスルホネート、ベンゼンスルホネート、10-カンファースルホネート、2-トリフルオロメチルベンゼンスルホネート、4-トリフルオロメチルベンゼンスルホネート、2,4-ジフルオロベンゼンスルホネート、パーフルオロベンゼンスルホネート、2-(ビシクロ[2.2.1]ヘプタン-2-イル)-1,1-ジフルオロエタンスルホネート、2-(ビシクロ[2.2.1]ヘプタン-2-イル)エタンスルホネートを挙げることができる。
ジスルホニルメタン化合物としては、例えば、下記式(12)で表される化合物を挙げることができる。
これらの他の酸発生剤は、単独でまたは2種以上を混合して使用することができる。
また、スルホニルオキシイミド化合物、スルホニルジアゾメタン化合物、およびフッ素原子で置換されていてもよいベンゼンスルホン酸を発生するオニウム塩化合物以外の酸発生剤の使用割合は、酸発生剤(B)の全量に対して、通常、30質量%以下、好ましくは10質量%以下である。この場合、他の酸発生剤の使用割合が30質量%をこえると、本発明の所期の効果が損なわれるおそれがある。
酸拡散制御剤:
酸拡散制御剤は、露光により酸発生剤(B)から生じる酸の、レジスト被膜中における拡散現象を制御し、非露光領域における好ましくない化学反応を抑制する作用を有する成分である。
このような酸拡散制御剤を含有させることにより、得られる感放射線性組成物の貯蔵安定性が向上する。また、形成したレジスト被膜の解像度が更に向上するとともに、露光後、加熱処理を行なうまでの引き置き時間(PED)の変動に起因するレジストパターンの線幅変化を抑えることができ、プロセス安定性に極めて優れた感放射線性組成物が得られる。
含窒素有機化合物としては、例えば、下記式(14)で表される化合物(以下、「含窒素化合物(i)」という)、下記式(15)で表される同一分子内に窒素原子を2個有する化合物(以下、「含窒素化合物(ii)」という)、窒素原子を3個以上有するポリアミノ化合物や重合体(以下、これらをまとめて「含窒素化合物(iii)」という)、下記式(16)で表されるアミド基含有化合物、ウレア化合物、含窒素複素環化合物等を挙げることができる。
含窒素化合物(i)としては、ジ(シクロ)アルキルアミン類、トリ(シクロ)アルキルアミン類、トリアルコールアミン等の置換アルキルアミン類、アニリン類等の芳香族アミン類を挙げることができる。
含窒素化合物(iii)としては、例えば、トリアジン類、ポリエチレンイミン、ポリアリルアミン、2-ジメチルアミノエチルアクリルアミドの重合体等を挙げることができる。
含窒素複素環化合物としては、例えば、イミダゾール類、ピリジン類、ピペラジン類、ピペリジン類、トリアジン類、モルホリン類のほか、ピラジン、ピラゾール、ピリダジン、キノザリン、プリン、ピロリジン、1,4-ジアザビシクロ[2.2.2]オクタン等を好適例として挙げることができる。
酸拡散制御剤の配合量は、酸解離性基含有樹脂(A)100質量部当り、通常、15質量部以下、好ましくは0.001~10質量部、更に好ましくは0.005~5質量部である。この場合、酸拡散制御剤の配合量が15質量部をこえると、レジストとしての感度や露光部の現像性が低下する傾向がある。なお、酸拡散制御剤の配合量が0.001質量部未満では、プロセス条件によっては、レジストとしてのパターン形状や寸法忠実度が低下するおそれがある。
このような界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンn-オクチルフェノールエーテル、ポリオキシエチレンn-ノニルフェノールエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート等を挙げることができ、また市販品としては、商品名で、例えば、エフトップEF301、同EF303、同EF352(トーケムプロダクツ社製)、メガファックス F171、同 F173(大日本インキ化学工業(株)製)、フロラードFC430、同FC431(住友スリーエム(株)製)、アサヒガードAG710、サーフロンS-382、同SC101、同SC102、同SC103、同SC104、同SC105、同SC106(旭硝子(株)製)、KP341(信越化学工業(株)製)、ポリフローNo.75、同No.95(共栄社化学(株)製)等を挙げることができる。
前記界面活性剤は、単独でまたは2種以上を混合して使用することができる。
界面活性剤の配合量は、酸解離性基含有樹脂(A)100質量部当り、通常、2質量部以下である。
組成物溶液の調製に使用される溶剤としては、例えば、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノ-n-プロピルエーテルアセテート、エチレングリコールモノ-n-ブチルエーテルアセテート等のエチレングリコールモノアルキルエーテルアセテート類;プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ-n-プロピルエーテル、プロピレングリコールモノ-n-ブチルエーテル等のプロピレングリコールモノアルキルエーテル類;プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールジ-n-プロピルエーテル、プロピレングリコールジ-n-ブチルエーテル等のプロピレングリコールジアルキルエーテル類;プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノ-n-プロピルエーテルアセテート、プロピレングリコールモノ-n-ブチルエーテルアセテート等のプロピレングリコールモノアルキルエーテルアセテート類;
等を挙げることができる。
これらの溶剤は、単独でまたは2種以上を混合して使用することができる。
合成例1
下記式(L-1)で表される化合物103g(70モル%)、下記式(L-2)で表される化合物40g(25モル%)、下記式(L-3)で表される化合物5g(5モル%)、アゾビスイソブチロニトリル(AIBN)6gおよびt-ドデシルメルカプタン1gを、プロピレングリコールモノメチルエーテル160gに溶解したのち、窒素雰囲気下、反応温度を70℃に保持して、16時間重合した。重合後、反応溶液を大量のn-ヘキサン中に滴下して、生成重合体を凝固精製した。
次いで、この精製重合体に、再度プロピレングリコールモノメチルエーテル150gを加えたのち、更にメタノール300g、トリエチルアミン80gおよび水15gを加えて、沸点にて還流させながら、8時間加水分解反応を行なった。反応後、溶剤およびトリエチルアミンを減圧留去し、得られた重合体をアセトンに溶解したのち、大量の水中に滴下して凝固させ、生成した白色粉末をろ過して、減圧下50℃で一晩乾燥した。
得られた重合体は、Mw=16,000、Mw/Mn=1.7であった。また、13C-NMR分析の結果、下記式(A1-1)で表される繰り返し単位を有し、それぞれの繰り返し単位の含有率(モル比)は、a/b/c=72.2/23.1/4.7であった。この重合体を樹脂(A1-1)とする。
上記式(L-1)で表される化合物174g(75モル%)、上記式(L-2)で表される化合物55g(22モル%)、下記式(L-4)で表される化合物11g(3モル%)、AIBN14gおよびt-ドデシルメルカプタン11gを、プロピレングリコールモノメチルエーテル240gに溶解したのち、窒素雰囲気下、反応温度を70℃に保持して、16時間重合した。重合後、反応溶液を大量のn-ヘキサン中に滴下して、生成重合体を凝固精製し、減圧下50℃で3時間乾燥した。
次いで、この精製重合体190gに、再度プロピレングリコールモノメチルエーテル150gを加えたのち、更にメタノール300g、トリエチルアミン100gおよび水15gを加えて、沸点にて還流させながら、8時間加水分解反応を行なった。反応後、溶剤およびトリエチルアミンを減圧留去し、得られた重合体をアセトンに溶解したのち、大量の水中に滴下して凝固させ、生成した白色粉末をろ過して、減圧下50℃で一晩乾燥した。
得られた重合体は、Mw=27,000、Mw/Mn=2.6であった。また、13C-NMR分析の結果、下記式(A1-2)で表される繰り返し単位を有し、それぞれの繰り返し単位の含有率(モル比)は、a/b/c=75.3/21.8/2.9であった。この重合体を樹脂(A1-2)とする。
共重合モル比90:10のp-ヒドロキシスチレン/p-t-ブトキシスチレン共重合体25gを、酢酸n-ブチル100gに溶解し、窒素ガスにより30分問バブリングを行なったのち、エチルビニルエーテル3.3gを加え、触媒としてp-トルエンスルホン酸ピリジニウム塩1gを加えて、室温で12時間反応させた。その後、反応溶液を1質量%アンモニア水溶液中に滴下して、重合体を凝固させて、ろ過したのち、減圧下50℃で一晩乾燥した。
得られた重合体は、Mwが13,000、Mw/Mnが1.01であった。また、13C-NMR分析の結果、下記式(A1-3)で表される繰り返し単位を有し、それぞれの繰り返し単位の含有率(モル比)は、a/b/c=66.7/9.9/23.4であった。この重合体を樹脂(A1-3)とする。
上記式(L-1)で表される化合物150g(65モル%)、上記式(L-2)で表される化合物25g(10モル%)、下記式(L-5)で表される化合物65g(25モル%)、AIBN14gおよびt-ドデシルメルカプタン11gを、プロピレングリコールモノメチルエーテル240gに溶解したのち、窒素雰囲気下、反応温度を70℃に保持して、16時間重合した。重合後、反応溶液を大量のn-ヘキサン中に滴下して、生成重合体を凝固精製し、減圧下50℃で3時間乾燥した。
次いで、この精製重合体190gに、再度プロピレングリコールモノメチルエーテル150gを加えたのち、更にメタノール300g、トリエチルアミン100gおよび水15gを加えて、沸点にて還流させながら、8時間加水分解反応を行なった。反応後、溶剤およびトリエチルアミンを減圧留去し、得られた重合体をアセトンに溶解したのち、大量の水中に滴下して凝固させ、生成した白色粉末をろ過して、減圧下50℃で一晩乾燥した。
得られた重合体は、Mw=16,000、Mw/Mn=1.6であった。また、13C-NMR分析の結果、下記式(A1-2)で表される繰り返し単位を有し、それぞれの繰り返し単位の含有率(モル比)は、a/b/c=66.7/8.9/24.4であった。この重合体を樹脂(A1-4)とする。
下記式(L-6)で表される化合物54g(50モル%)、下記式(L-7)で表される化合物11g(10モル%)、および上記式(L-5)で表される化合物35g(40モル%)を200gの2-ブタノンに溶解し、AIBN5.58gを更に投入して単量体溶液を調製した。100gの2-ブタノンを投入した1000mLの三口フラスコを30分窒素パージした後、撹拌しながら80℃に加熱し、調製した単量体溶液を滴下漏斗にて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。重合反応終了後、重合溶液を水冷することにより、30℃以下に冷却した後、2000g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のメタノールを用いてスラリー上で2回洗浄した後、ろ別し、50℃で17時間乾燥させて白色粉末の重合体を得た(74g、収率74%)。得られた重合体のMwは6,900であり、Mw/Mnは1.70であった。また、13C-NMR分析の結果、下記式(A2-1)で表される繰り返し単位を有し、それぞれの繰り返し単位の含有率(モル比)は、a/b/c=53.0/9.8/37.2であった。この重合体を樹脂(A2-1)とする。
上記式(L-6)で表される化合物54g(50モル%)、上記式(L-7)で表される化合物11g(10モル%)、および下記式(L-8)で表される化合物35g(40モル%)を200gの2-ブタノンに溶解し、AIBN5.58gを更に投入して単量体溶液を調製した。100gの2-ブタノンを投入した1000mLの三口フラスコを30分窒素パージした後、撹拌しながら80℃に加熱し、調製した単量体溶液を滴下漏斗にて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。重合反応終了後、重合溶液を水冷することにより、30℃以下に冷却した後、2000g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のメタノールを用いてスラリー上で2回洗浄した後、ろ別し、50℃で17時間乾燥させて白色粉末の重合体を得た(74g、収率74%)。得られた重合体のMwは8,000であり、Mw/Mnは1.70であった。また、13C-NMR分析の結果、下記式(A2-2)で表される繰り返し単位を有し、それぞれの繰り返し単位の含有率(モル比)は、a/b/c=49.8/10.0/40.2であった。この重合体を樹脂(A2-2)とする。
上記式(L-7)で表される化合物の代わりに、下記式(L-9)で表される化合物39g(37モル%)を使用したこと、上記式(L-6)で表される化合物50g(50モル%)を使用したこと、および上記式(L-5)で表される化合物11g(13モル%)を使用したこと以外は、合成例5と同様にして重合体を得た(78g、収率78%)。得られた重合体のMwは5,200であり、Mw/Mnは1.62であった。また、13C-NMR分析の結果、式(A2-3)で表される繰り返し単位を有し、それぞれの繰り返し単位の含有率(モル比)は、a/b/c=50.0/37.0/13.0であった。この重合体を樹脂(A2-3)とする。
上記式(L-7)で表される化合物の代わりに下記式(L-10)で表される化合物10g(10モル%)を使用したこと、上記式(L-6)で表される化合物55g(50モル%)を使用したこと、および上記式(L-5)で表される化合物36g(40モル%)を使用したこと以外は、合成例5と同様にして重合体を得た(71g、収率71%)。得られた重合体のMwは8,100であり、Mw/Mnは1.69であり、低分子量成分の残存割合は0.04%であった。また、13C-NMR分析の結果、式(A2-4)で表される繰り返し単位を有し、それぞれの繰り返し単位の含有率(モル比)は、a/b/c=53.6/9.8/36.6であった。この重合体を樹脂(A2-4)とする。
上記式(L-6)で表される化合物55g(50モル%)および上記式(L-5)で表される化合物45g(50モル%)を使用したこと以外は、合成例5と同様にして重合体を得た(71g、収率71%)。得られた重合体のMwは7,000であり、Mw/Mnは1.65であった。また、13C-NMR分析の結果、式(A2-5)で表される繰り返し単位を有し、それぞれの繰り返し単位の含有率(モル比)は、a/b=50.9/49.1であった。この重合体を樹脂(A2-5)とする。
上記式(L-6)で表される化合物49g(50モル%)を使用したこと、上記式(L-9)で表される化合物36g(35モル%)を使用したこと、および下記式(L-11)で表される化合物16g(15モル%)を使用したこと以外は、合成例4と同様に合成し、重合体(A2-5)を得た(79g、収率79%)。得られた重合体のMwは9,500であり、Mw/Mnは1.55であった。また、13C-NMR分析の結果、式(A2-6)で表される繰り返し単位を有し、それぞれの繰り返し単位の含有率(モル比)は、a/b/c=49.0/37.0/14.0であった。この重合体を樹脂(A2-6)とする。
感度:
図1に示すように、シリコン基板1上に高さ100nmおよび線幅90nmで、スペース180nmのポリシリコンの段差2を作成したウェハを準備した。このウェハ上に、図2に示すように、ポリシリコンの段差2と直交するレジストパターン3の線幅180nmライン・アンド・スペースパターン(1L1S)を1対1の線幅に形成する露光量を最適露光量とし、この最適露光量を感度とした。
スカムマージン:
図2に示した最適露光量で露光したときのレジストパターンの拡大図を図3に示す。レジストパターン3と段差2が交差する部位付近の露光部に生ずるスカム4のレジストパターンとスカム端の幅tを測定し、10nm以下であれば良好、10nmをこえる場合は不良と定義した。
形状:
レジストパターンを後述のCD(Critical Dimension)-走査型電子顕微鏡で観察し、最適露光量で露光したときのレジストパターンのラインパターンのホワイトエッジ(エッジの欠け)が5nm以下であれば良好、5nmをこえる場合は不良と定義した。
表1(但し、部は質量に基づく。)に示す各成分を混合して均一溶液としたのち、孔径0.2μmのテフロン(登録商標)製メンブレンフィルターでろ過して、組成物溶液を調製した。
次いで、各組成物溶液を、シリコンウエハー上に回転塗布したのち、110℃で90秒間PBを行なって、膜厚0.3μmのレジスト被膜を形成した。その後、各レジスト被膜に、KrFエキシマレーザー照射装置NSR-S203B(商品名、(株)ニコン製)を用い、KrFエキシマレーザー(波長248nm)をマスクパターンを介し露光量を変えて露光したのち、110℃で90秒間PEBを行なった。その後、2.38質量%テトラメチルアンモニウムヒドロキシド水溶液を現像液として用い、23℃で60秒間現像したのち、水で30秒間洗浄し、乾燥して、レジストパターンを形成した。レジストパターンはCD-走査型電子顕微鏡S-9220(商品名、(株)日立ハイテクノロジース製)を用いて観察した。
各実施例および比較例の評価結果を、表2に示す。
酸発生剤(B)
B-1:N-(トリフルオロメタンスルホニルオキシ)ビシクロ[2.2.1]ヘプト-5-エン-2,3-ジカルボキシイミド
B-2:ビス(シクロヘキサンスルホニル)ジアゾメタン
B-3:N-(10-カンファースルホニルオキシ)スクシンイミド
B-4:2,4,6-トリメチルフェニルジフェニルスルホニウム2,4-ジフルオロベンゼンスルホネート
B-5:トリフェニルスルホニウムベンゼンスルホネート
B-6:トリフェニルスルホニウムノナフルオロブタンスルホネート
酸拡散制御剤
C-1:2-フェニルベンズイミダゾール
溶剤
D-1:乳酸エチル
D-2:プロピレングリコールモノメチルエーテルアセテート
D-3:3-エトキシプロピオン酸エチル
2 ポリシリコンの段差
3 レジストパターン
4 スカム
Claims (10)
- 下記式(1)で表される繰り返し単位を含む重合体(A1)と、下記式(2)で表される繰り返し単位を含み、かつ前記式(1)で表される繰り返し単位を含まない重合体(A2)とを含む重合体(A)と、感放射線性酸発生剤(B)とを含有することを特徴とする感放射線性組成物。
式(2)において、R3は、水素原子またはメチル基を表し、R4は、(i)相互に独立に、炭素数4~20の1価の脂環式炭化水素基もしくはその誘導体、または炭素数1~4の直鎖状もしくは分岐状のアルキル基を表すか、または、(ii)いずれか二つのR4が相互に結合して形成される、それぞれが結合している炭素原子を含む炭素数4~20の2価の脂環式炭化水素基またはその誘導体を表し、残りのR4が、炭素数1~4の直鎖状もしくは分岐状のアルキル基、または炭素数4~20の1価の脂環式炭化水素基もしくはその誘導体を表す。) - 前記重合体(A1)は酸解離性基を有する繰り返し単位を含むことを特徴とする請求項1記載の感放射線性組成物。
- 前記重合体(A2)は、下記式(3-1)、式(3-2)および式(3-3)から選ばれる少なくとも1つで表される繰り返し単位を含有することを特徴とする請求項1記載の感放射線性組成物。
- 前記重合体(A)の合計を100質量%としたとき、前記重合体(A2)は1~50質量%含有することを特徴とする請求項1記載の感放射線性組成物。
- 前記感放射線性酸発生剤(B)は、非イオン性感放射線性酸発生剤を含むことを特徴とする請求項1記載の感放射線性組成物。
- 前記非イオン性感放射線性酸発生剤が、スルホニルオキシイミド化合物であることを特徴とする請求項7記載の感放射線性組成物。
- 前記非イオン性感放射線性酸発生剤が、スルホニルジアゾメタン化合物であることを特徴とする請求項7記載の感放射線性組成物。
- 前記感放射線性酸発生剤(B)が、更にフッ素原子で置換されていてもよいベンゼンスルホン酸を発生するオニウム塩化合物を含むことを特徴とする請求項7記載の感放射線性組成物。
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JP2013080006A (ja) * | 2011-09-30 | 2013-05-02 | Fujifilm Corp | パターン形成方法、感電子線性又は感極紫外線性樹脂組成物、及び、レジスト膜、並びに、これらを用いた電子デバイスの製造方法、及び、電子デバイス |
JP2013222061A (ja) * | 2012-04-16 | 2013-10-28 | Tokyo Ohka Kogyo Co Ltd | レジストパターン形成方法 |
JP2014021470A (ja) * | 2012-07-24 | 2014-02-03 | Sumitomo Chemical Co Ltd | レジスト組成物及びレジストパターンの製造方法 |
JP2014170219A (ja) * | 2013-02-08 | 2014-09-18 | Sumitomo Chemical Co Ltd | レジスト組成物及びレジストパターンの製造方法 |
JP2015232607A (ja) * | 2014-06-09 | 2015-12-24 | 信越化学工業株式会社 | 化学増幅ポジ型レジスト材料及びパターン形成方法 |
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JP7344108B2 (ja) * | 2019-01-08 | 2023-09-13 | 信越化学工業株式会社 | レジスト組成物、及びパターン形成方法 |
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