WO2011062168A1 - 感放射線性樹脂組成物、重合体及びレジストパターン形成方法 - Google Patents
感放射線性樹脂組成物、重合体及びレジストパターン形成方法 Download PDFInfo
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- WO2011062168A1 WO2011062168A1 PCT/JP2010/070412 JP2010070412W WO2011062168A1 WO 2011062168 A1 WO2011062168 A1 WO 2011062168A1 JP 2010070412 W JP2010070412 W JP 2010070412W WO 2011062168 A1 WO2011062168 A1 WO 2011062168A1
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- 0 CC*1CCC(C)(C)CC1 Chemical compound CC*1CCC(C)(C)CC1 0.000 description 2
- JZDSOQSUCWVBMV-UHFFFAOYSA-N CCN(C(c1ccccc11)=O)C1=O Chemical compound CCN(C(c1ccccc11)=O)C1=O JZDSOQSUCWVBMV-UHFFFAOYSA-N 0.000 description 1
Classifications
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
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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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—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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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
Definitions
- the present invention relates to a radiation sensitive resin composition, a polymer, and a resist pattern forming method.
- lithography technology capable of microfabrication at a level of 0.10 ⁇ m or less (sub-quarter micron level) is eagerly desired.
- the conventional lithography technique uses near ultraviolet rays such as i-rays as radiation, the above-mentioned fine processing is extremely difficult. Therefore, in order to enable fine processing at the above level, development of lithography technology using radiation having a shorter wavelength is being carried out.
- the radiation having a shorter wavelength include an emission line spectrum of a mercury lamp, an excimer laser and other far ultraviolet rays, an X-ray, an electron beam, and the like.
- a KrF excimer laser wavelength 248 nm
- an ArF excimer laser A wavelength of 193 nm
- a material for example, a component having an acid-dissociable group and a component that generates an acid upon irradiation with radiation (hereinafter also referred to as “exposure”) (hereinafter also referred to as “acid generator”). And a composition using these chemical amplification effects (hereinafter also referred to as “chemically amplified resist”) and the like (see Patent Documents 1 and 2).
- exposure a component having an acid-dissociable group and a component that generates an acid upon irradiation with radiation
- exposure hereinafter also referred to as “acid generator”
- chemically amplified resist a composition using these chemical amplification effects
- Patent Documents 1 and 2 see Patent Documents 1 and 2
- an acid-dissociable group present in the resin is dissociated by the action of an acid generated by exposure, and the resin has an acidic group or the like.
- the exposed region of the resist film becomes readily soluble in an alkali developer, so that a desired resist pattern can be formed.
- a finer resist pattern for example, a fine resist pattern having a line width of about 45 nm.
- Examples of a method for making it possible to form a finer resist pattern include shortening the light source wavelength of the exposure apparatus and increasing the numerical aperture (NA) of the lens.
- NA numerical aperture
- a new exposure apparatus is required to shorten the wavelength of the light source, but such an apparatus is expensive.
- the numerical aperture of the lens is increased, the resolution and the depth of focus are in a trade-off relationship. Therefore, there is an inconvenience that the depth of focus decreases even if the resolution can be improved.
- liquid immersion lithography liquid immersion lithography
- an immersion exposure liquid for example, pure water or a fluorine-based inert liquid
- the exposure optical path space that has been conventionally filled with an inert gas such as air or nitrogen is filled with the immersion exposure liquid having a refractive index (n) larger than that of air or the like.
- the present invention has been made in view of the above circumstances, and a radiation-sensitive resin composition capable of obtaining a good pattern shape, excellent in MEEF performance, and capable of suppressing the occurrence of defects such as bridges, and the like. It aims at providing the resist pattern formation method using the polymer which can be used suitably for photosensitive resin composition, and this radiation sensitive resin composition.
- the inventors of the present invention have made extensive studies to solve the above problems, and as a result, the radiation-sensitive resin composition contains a fluorine-containing polymer having a structural unit containing a specific acid-dissociable group.
- the inventors have found that the above-mentioned problems can be solved, and have completed the present invention.
- the invention made to solve the above problems is [A] having at least one structural unit (I) selected from the group consisting of a plurality of structural units respectively represented by the following formulas (1-1) and (1-2), and having a fluorine atom content 5% by mass or more of a polymer (hereinafter also referred to as “[A] polymer”), [B] a polymer having an acid dissociable group and a fluorine atom content of less than 5% by mass (hereinafter also referred to as “[B] polymer”), and [C] a radiation-sensitive acid generator ( Hereinafter also referred to as “[C] acid generator”.) Is a radiation-sensitive resin composition.
- each R 1 independently represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group.
- Y represents a (2 + d) -valent saturated hydrocarbon group.
- R 2 and R 3 are each independently an alkyl group. However, R 2 and R 3 may be bonded to each other to form an alicyclic structure together with Y.
- R 4 is an alkyl group, an alkoxy group, an acyl group, or an acyloxy group. When a plurality of R 3 or R 4 are present, the plurality of R 3 and R 4 may be the same or different. Some or all of the hydrogen atoms of R 4 may be substituted.
- a is 1 or 2.
- R 5 represents an alkyl group.
- R 6 is an alkyl group, an alkoxy group, an acyl group, or an acyloxy group. If R 6 there are a plurality, the plurality of R 6 may be the same or different. Some or all of the hydrogen atoms of the R 6 may be substituted.
- e is 1 or 2.
- f is an integer of 0 to 5.
- the radiation-sensitive resin composition has the above-mentioned specific structural unit (I) in addition to the [B] polymer and [C] acid generator as a base polymer for forming a resist film, and has a fluorine atom content.
- the [A] polymer has a structural unit containing an acid-dissociable group having the above specific structure, the radiation-sensitive resin composition is excellent in MEEF performance and suppresses the occurrence of defects such as bridges. be able to.
- the reason why the above-described configuration improves the MEEF performance and the defect suppression performance such as bridges of the radiation-sensitive resin composition is not necessarily clear, but is considered as follows, for example.
- the acid dissociable group of the polymer has an alicyclic structure and a hydrocarbon group bonded to a carbon atom adjacent to the oxygen atom of the ester group. It is considered that the acid dissociable group is likely to be dissociated by an acid because of the specific relationship between the number of carbon atoms in the ring of the alicyclic structure and the structure of the hydrocarbon group. Therefore, it is considered that the contrast of the dissolution rate between the exposed part and the unexposed part is increased, and the MEEF performance is improved.
- the solubility of the resist film surface layer in the exposed portion in the developer is increased. Conceivable. As a result, the ability to suppress defects such as bridges is improved.
- the polymer may further have at least one structural unit (II) selected from the group consisting of a plurality of structural units respectively represented by the following formulas (2-1) to (2-3). preferable.
- R 1 represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group.
- Rf 1 is a fluorinated hydrocarbon group having 1 to 30 carbon atoms.
- R 7 is a (g + 1) -valent linking group.
- R 8 is a hydrogen atom or a monovalent organic group. If R 8 there are a plurality, the plurality of R 8 may be the same or different.
- Rf 2 and Rf 3 are each independently a hydrogen atom, a fluorine atom or a fluorinated hydrocarbon group having 1 to 30 carbon atoms. However, there is no case where both Rf 2 and Rf 3 are hydrogen atoms. When a plurality of Rf 2 or Rf 3 are present, the plurality of Rf 2 and Rf 3 may be the same or different.
- g is an integer of 1 to 3.
- R 9 is a divalent linking group.
- R 10 is hydrogen atom or a monovalent organic group.
- Rf 4 and Rf 5 are each independently a hydrogen atom, a fluorine atom or a fluorinated hydrocarbon group having 1 to 30 carbon atoms. However, there is no case where both Rf 4 and Rf 5 are hydrogen atoms. )
- the polymer further has the above-mentioned specific structural unit having a fluorine atom, so that the elution suppression property to the immersion exposure liquid such as an acid generator in the resist film, and the resist film and the immersion exposure liquid The receding contact angle can be increased efficiently. As a result, it is possible to further suppress the occurrence of defects due to the immersion exposure liquid.
- the polymer is a structural unit containing at least one group selected from the group consisting of a plurality of groups represented by the following formulas (4-1) and (4-2) (the above formula (2- It is preferable to further include (excluding the structural unit represented by 3).
- R 41 is a hydrocarbon group having 1 to 10 carbon atoms substituted with a fluorine atom.
- the polymer When the polymer further has a structural unit containing the specific alkali-soluble group, the solubility of the [A] polymer in the developer is improved. As a result, the MEEF of the radiation-sensitive resin composition is improved. The performance and the ability to suppress defects such as bridges can be further improved.
- the content of the [A] polymer with respect to 100 parts by mass of the polymer is preferably 0.1 parts by mass or more and 20 parts by mass or less.
- the polymer of the present invention is: Having at least one structural unit (I) selected from the group consisting of a plurality of structural units represented by the following formulas (1-1) and (1-2), respectively, and having a fluorine atom content of 5% by mass That's it.
- each R 1 independently represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group.
- Y represents a (2 + d) -valent saturated hydrocarbon group.
- R 2 and R 3 are each independently an alkyl group. However, R 2 and R 3 may be bonded to each other to form an alicyclic structure together with Y.
- R 4 is an alkyl group, an alkoxy group, an acyl group or an acyloxy group. When a plurality of R 3 or R 4 are present, the plurality of R 3 and R 4 may be the same or different. Some or all of the hydrogen atoms of R 4 may be substituted. a is 1 or 2. b is an integer of 0 to 3. d is 1 or 2. In formula (1-2), R 5 represents an alkyl group. R 6 is an alkyl group, an alkoxy group, an acyl group, or an acyloxy group. If R 6 there are a plurality, the plurality of R 6 may be the same or different. A part or all of the hydrogen atoms of R 6 may be substituted. e is 1 or 2. f is an integer of 0 to 5. )
- the polymer preferably further has at least one structural unit (II) selected from the group consisting of a plurality of structural units each represented by the following formulas (2-1) to (2-3).
- R 1 represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group.
- Rf 1 is a fluorinated hydrocarbon group having 1 to 30 carbon atoms.
- R 7 is a (g + 1) -valent linking group.
- R 8 is a hydrogen atom or a monovalent organic group. If R 8 there are a plurality, the plurality of R 8 may be the same or different.
- Rf 2 and Rf 3 are each independently a hydrogen atom, a fluorine atom or a fluorinated hydrocarbon group having 1 to 30 carbon atoms. However, there is no case where both Rf 2 and Rf 3 are hydrogen atoms. When a plurality of Rf 2 or Rf 3 are present, the plurality of Rf 2 and Rf 3 may be the same or different.
- g is an integer of 1 to 3.
- R 9 is a divalent linking group.
- R 10 is hydrogen atom or a monovalent organic group.
- Rf 4 and Rf 5 are each independently a hydrogen atom, a fluorine atom or a fluorinated hydrocarbon group having 1 to 30 carbon atoms. However, there is no case where both Rf 4 and Rf 5 are hydrogen atoms. )
- the polymer is a structural unit containing at least one group selected from the group consisting of groups represented by the following formulas (4-1) and (4-2) (represented by the above formula (2-3)). It is preferable to further include (In the formula (4-1), R 41 is a hydrocarbon group having 1 to 10 carbon atoms substituted with a fluorine atom.)
- the polymer has the structural unit (I), can further have the structural unit (II), and can further have the structural unit (IV).
- a polymer has the characteristics that when the fluorine atom content is a predetermined value or more, it can be unevenly distributed in the surface layer of the resist film and is easily dissolved in the developer after the action of acid. Therefore, the said polymer is suitable for the radiation sensitive resin composition etc. which are used for lithography technique, for example.
- the resist pattern forming method of the present invention comprises: (1) forming a photoresist film on a substrate using the radiation sensitive resin composition; (2) a step of disposing an immersion exposure liquid on the photoresist film and subjecting the photoresist film to immersion exposure via the immersion exposure liquid; and (3) the immersion-exposed photoresist. And developing a film to form a resist pattern.
- the radiation-sensitive resin composition is used as the photoresist composition, a resist pattern having excellent MEEF performance and few defects such as bridges can be obtained.
- the radiation-sensitive resin composition of the present invention a good pattern shape can be obtained, the MEEF performance is excellent, and defects such as bridges are hardly generated. Furthermore, since the formed resist film surface is excellent in water repellency and has a high receding contact angle, it can be suitably used in the immersion exposure process without further forming a protective film on the upper surface of the resist film. . For this reason, it can be suitably used in lithography technology that will be miniaturized in the future.
- (meth) acryl means acryl and / or methacryl.
- the radiation sensitive resin composition of this invention contains a [A] polymer, a [B] polymer, and a [C] acid generator. Moreover, the said radiation sensitive resin composition may contain arbitrary components in the range which does not impair the effect of this invention. The said radiation sensitive resin composition can obtain a favorable pattern shape, is excellent in MEEF performance, and does not produce a bridge defect etc. easily. Hereinafter, each component will be described.
- the polymer has at least one structural unit (I) selected from the group consisting of a plurality of structural units represented by the above formulas (1-1) and (1-2). It is a polymer having an atomic content of 5% by mass or more.
- the polymer contains a predetermined amount or more of fluorine atoms, when a resist film is formed from the radiation-sensitive resin composition, its distribution depends on the oil-repellent characteristics of the [A] polymer in the film. Tends to be high on the resist coating surface. Therefore, at the time of immersion exposure, it is possible to suppress the acid generator, the acid diffusion control agent, and the like in the resist film from eluting into the immersion exposure liquid such as water.
- the structural unit (I) is at least one structural unit selected from the group consisting of a plurality of structural units represented by the above formulas (1-1) and (1-2).
- R 1 each independently represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group.
- Y is a (2 + d) -valent saturated hydrocarbon group.
- R 2 and R 3 are each independently an alkyl group. However, R 2 and R 3 may be bonded to each other to form an alicyclic structure together with Y.
- R 4 is an alkyl group, an alkoxy group, an acyl group, or an acyloxy group. When a plurality of R 3 or R 4 are present, the plurality of R 3 and R 4 may be the same or different. Some or all of the hydrogen atoms of R 4 may be substituted.
- a is 1 or 2.
- R 5 is an alkyl group.
- R 6 is an alkyl group, an alkoxy group, an acyl group, or an acyloxy group. If R 6 there are a plurality, the plurality of R 6 may be the same or different. A part or all of the hydrogen atoms of R 6 may be substituted.
- e is 1 or 2.
- f is an integer of 0 to 5.
- the lower alkyl group represented by R 1 is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group. Group, 2- (2-methylpropyl) group and the like. Among these, a methyl group is particularly preferable.
- the halogenated lower alkyl group represented by R 1 is preferably a C 1-4 alkyl group having a halogen atom.
- a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
- the halogenated lower alkyl group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a trichloromethyl group, a tribromomethyl group, and a triiodo.
- a methyl group etc. are mentioned. Among these, a fluorinated alkyl group having 1 to 4 carbon atoms is more preferable, and a trifluoromethyl group is more preferable.
- Examples of the alkyl group represented by R 2 and R 3 , R 4 and R 6 and R 5 include methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, 2 -(2-methylpropyl) group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 1- (2-methylbutyl) group, 1- (3-methylbutyl) group, 2- (2-methylbutyl) group 2- (3-methylbutyl) group, neopentyl group, 1-hexyl group, 2-hexyl group, 3-hexyl group, 1- (2-methylpentyl) group, 1- (3-methylpentyl) group, 1- (4-methylpentyl) group, 2- (2-methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methylpentyl) group, 3- (2-methylpentyl) group, 3- (3-methylpentyl) group, etc.
- cyclopentyl group cyclopentylmethyl group, 1- (1-cyclopentylethyl) group, 1- (2-cyclopentylethyl) group, cyclohexyl group, cyclohexylmethyl group, 1- (1-cyclohexylethyl) Group, 1- (2-cyclohexylethyl group), cycloheptyl group, cycloheptylmethyl group, 1- (1-cycloheptylethyl) group, 1- (2-cycloheptylethyl) group, 2-norbornyl group, etc.
- Examples thereof include cyclic alkyl groups of several 4 to 20.
- R 2 is preferably a methyl group, an ethyl group, or a propyl group, and more preferably a methyl group.
- R 3 is preferably a methyl group or an ethyl group, and more preferably a methyl group.
- R 5 is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group or an n-butyl group, and a methyl group or More preferred is an ethyl group.
- R 4 and R 6 are preferably a methyl group and an ethyl group, and more preferably a methyl group.
- alkoxy group represented by R 4 and R 6 examples include alkoxy groups having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-butoxy group, a t-butoxy group, a propoxy group, and an isopropoxy group. Can be mentioned.
- the acyl group represented by R 4 and R 6, for example, acetyl group, ethylcarbonyl group, and an acyl group having 1 to 10 carbon atoms such as propyl group.
- Examples of the acyloxy group represented by R 4 and R 6 include an acetoxy group, an ethylyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group, an n-hexane carbonyloxy group, and an n-octane carbonyloxy group. And an acyloxy group having 1 to 10 carbon atoms such as a group.
- Examples of the (2 + d) -valent saturated hydrocarbon group represented by Y include a group obtained by removing (1 + d) hydrogen atoms from the linear, branched, or cyclic alkyl group. Among these, a methanediyl group and a methanetriyl group are preferable, and a methanediyl group is more preferable.
- d is 1 or 2, but is more preferably 1.
- Examples of the alicyclic structure formed by combining R 2 and R 3 together with Y include a cyclopentane structure, a methylcyclopentane structure, an ethylcyclopentane structure, a cyclohexane structure, a methylcyclohexane structure, an ethylcyclohexane structure, and a cycloheptane structure. , Methylcycloheptane structure, ethylcycloheptane structure, norbornane structure and the like.
- R 4 and R 6 may have include a halogen atom such as a cyano group, a fluorine atom, a chlorine atom, and a bromine atom, a phenyl group, a hydroxyl group, an acyloxy group, and an alkoxy group. It is done.
- Examples of groups formed from the above R 2 , R 3 and Y include 2-propyl group, 2-butyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl group and the like.
- Secondary alkyl group; tertiary alkyl groups such as 1,1-dimethylethyl group, 1,1-dimethylpropyl group, 1-ethyl-1-methylpropyl group and the like can be mentioned.
- 2-propyl group, 2-butyl group, 1,1-dimethylethyl group, and 1,1-dimethyl group are selected from the viewpoint of increasing the ease of dissociation of the acid-dissociable group of structural unit (I-1).
- a propyl group is preferred, a 2-propyl group and a 2-butyl group are more preferred, and a 2-propyl group is particularly preferred.
- the monomer that gives the structural unit (I) include (meth) acrylic acid 1-isopropyl-1-cyclopentyl ester, (meth) acrylic acid 1-tert-butyl-1-cyclopentyl ester, (Meth) acrylic acid 1-isopropyl-1-cyclohexyl ester, (meth) acrylic acid 1-tert-butyl-1-cyclohexyl ester, (meth) acrylic acid 1-methyl-1-cycloheptyl ester, (meth) acrylic acid 1 -Ethyl-1-cycloheptyl ester, (meth) acrylic acid 1-isopropyl-1-cycloheptyl ester, (meth) acrylic acid 1-tert-butyl-1-cycloheptyl ester, (meth) acrylic acid 1-methyl- 1-cyclooctyl ester, (meth) acrylic acid 1-ethyl-1-cyclooctyl ester, (Meth) acrylic acid 1-isopropyl-1-cyclopent
- (meth) acrylic acid 1-isopropyl-1-cyclopentyl ester, (meth) acrylic acid 1-methyl-1-cycloheptyl ester, (meth) acrylic acid 1-ethyl-1-cyclohexane Heptyl ester, (meth) acrylic acid 1-methyl-1-cyclooctyl ester, and (meth) acrylic acid 1-ethyl-1-cyclooctyl ester are preferred.
- the polymer may contain only one type of structural unit (I), or may contain two or more types.
- the polymer contains at least one fluorine selected from the group consisting of a plurality of structural units represented by the above formulas (2-1) to (2-3) in addition to the structural unit (I). You may further have structural unit (II) which has an atom. [A] Since the polymer has the structural unit (II), the dissolution of the acid generator and the acid diffusion controller in the resist film from the immersion exposure liquid is suppressed, and the resist film and the immersion exposure liquid By improving the receding contact angle, liquid immersion liquid droplets are unlikely to remain on the resist film, and as a result, generation of defects due to the liquid immersion exposure liquid can be suppressed.
- the structural unit (II-1) is a structural unit represented by the above formula (2-1).
- R 1 is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group.
- Rf 1 is a fluorinated hydrocarbon group having 1 to 30 carbon atoms.
- Examples of the lower alkyl group and halogenated lower alkyl group represented by R 1 include the examples of R 1 in the above formulas (1-1) and (1-2).
- Examples of the fluorinated hydrocarbon group having 1 to 30 carbon atoms represented by Rf 1 include, for example, a linear or branched alkyl group having 1 to 6 carbon atoms substituted with at least one fluorine atom, at least 1 Examples thereof include a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms substituted with two fluorine atoms or a group derived therefrom.
- Examples of the linear or branched alkyl group having 1 to 6 carbon atoms substituted with at least one fluorine atom include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, 2-butyl group, 2- (2-methylpropyl) group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 1- (2-methylbutyl) group, 1- (3-methylbutyl) group, 2- (2-methylbutyl) group, 2- (3-methylbutyl) group, neopentyl group, 1-hexyl group, 2-hexyl group, 3-hexyl group, 1- (2-methylpentyl) group, 1- (3-methyl Pentyl) group, 1- (4-methylpentyl) group, 2- (2-methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methylpentyl) group, 3- (2-methyl) Pentyl) group
- Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms substituted with at least one fluorine atom represented by Rf 1 or a group derived therefrom include a cyclopentyl group, a cyclopentylmethyl group, 1 -(1-cyclopentylethyl) group, 1- (2-cyclopentylethyl) group, cyclohexyl group, cyclohexylmethyl group, 1- (1-cyclohexylethyl) group, 1- (2-cyclohexylethyl group), cycloheptyl group, Partially fluorinated or perfluorinated cycloaliphatic hydrocarbon groups such as cycloheptylmethyl, 1- (1-cycloheptylethyl), 1- (2-cycloheptylethyl), 2-norbornyl Mono groups and the like.
- Preferable monomers that give the structural unit (II-1) include, for example, (meth) acrylic acid trifluoromethyl ester, (meth) acrylic acid 2,2,2-trifluoroethyl ester, (meth) acrylic acid par Fluoroethyl ester, (meth) acrylic acid perfluoro n-propyl ester, (meth) acrylic acid perfluoro i-propyl ester, (meth) acrylic acid perfluoro n-butyl ester, (meth) acrylic acid perfluoro i-butyl ester Ester, (meth) acrylic acid perfluoro t-butyl ester, (meth) acrylic acid 2- (1,1,1,3,3,3-hexafluoropropyl) ester, (meth) acrylic acid 1- (2, 2,3,3,4,4,5,5-octafluoropentyl) ester, (meth) acrylic acid perful Rocyclohexylmethyl ester, (meth) acrylic acid 1- (2
- R 1 is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group.
- R 7 is a (g + 1) -valent linking group.
- R 8 is a hydrogen atom or a monovalent organic group. If R 8 there are a plurality, the plurality of R 8 may be the same or different.
- Rf 2 and Rf 3 are each independently a hydrogen atom, a fluorine atom or a fluorinated hydrocarbon group having 1 to 30 carbon atoms. However, there is no case where both Rf 2 and Rf 3 are hydrogen atoms.
- Rf 2 or Rf 3 When a plurality of Rf 2 or Rf 3 are present, the plurality of Rf 2 and Rf 3 may be the same or different.
- g is an integer of 1 to 3.
- R 9 is a divalent linking group.
- R 10 is a hydrogen atom or a monovalent organic group.
- Rf 4 and Rf 5 are each independently a hydrogen atom, a fluorine atom or a fluorinated hydrocarbon group having 1 to 30 carbon atoms. However, there is no case where both Rf 4 and Rf 5 are hydrogen atoms.
- R 8 and R 10 are a hydrogen atom or a monovalent organic group.
- the monovalent organic group include a monovalent hydrocarbon group having 1 to 30 carbon atoms, an acid dissociable group, and an alkali dissociable group.
- Examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms include a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms and a monovalent cyclic hydrocarbon group having 3 to 30 carbon atoms. Can be mentioned. As the explanation of these hydrocarbon groups, the explanation of R 4 and R 6 in the above formula (1-1) can be applied as they are (however, those corresponding to acid dissociable groups and alkali dissociable groups described later) Is excluded.)
- the said hydrocarbon group may have a substituent.
- substituents include those that may be possessed by R 4 and R 6 in the above formula (1-1).
- the “acid-dissociable group” refers to a group that substitutes a hydrogen atom in a polar functional group such as a hydroxyl group or a carboxyl group and dissociates in the presence of an acid.
- the acid dissociable group represented by R 8 and R 10 include t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, (thiotetrahydropyranylsulfanyl) methyl group, (thiotetrahydrofuran group).
- Nylsulfanyl) methyl group alkoxy-substituted methyl group, alkylsulfanyl-substituted methyl group and the like.
- the alkoxy group (substituent) in the alkoxy-substituted methyl group includes, for example, an alkoxy group having 1 to 4 carbon atoms.
- examples of the alkyl group (substituent) in the alkylsulfanyl-substituted methyl group include an alkyl group having 1 to 4 carbon atoms.
- examples of the acid dissociable group include a group represented by the formula [—C (R) 3 ].
- three Rs are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a derivative thereof. Or any two R's bonded to each other, together with the carbon atom to which each is bonded, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom. And one remaining R is a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a group derived therefrom. .
- Examples of the linear or branched alkyl group having 1 to 4 carbon atoms of R in the acid dissociable group represented by the above formula [—C (R) 3 ] include, for example, 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.
- Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms of R include cyclohexane such as norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane.
- Examples include a group obtained by removing one hydrogen from an alkane.
- Examples of the group derived from this alicyclic hydrocarbon group include a part or all of the hydrogen atoms of the above-mentioned monovalent alicyclic hydrocarbon group, for example, a methyl group, an ethyl group, an n-propyl group, i Linear, branched alkyl groups having 1 to 4 carbon atoms such as -propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group and t-butyl group, or cyclic groups having 4 to 20 carbon atoms And a group substituted with one or more of these alkyl groups.
- the alicyclic hydrocarbon group represented by R includes an alicyclic hydrocarbon formed from an alicyclic ring derived from norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane, or cyclohexane. And a group obtained by substituting part or all of the hydrogen atoms of the alicyclic hydrocarbon group with the alkyl group are preferred.
- any two R's are bonded to each other and formed with a carbon atom to which each R is bonded (a carbon atom bonded to an oxygen atom), and is a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms.
- a monocyclic hydrocarbon group such as a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, a cyclooctanediyl group, a norbornanediyl group, a tricyclodecanediyl group, or a tetracyclodecanediyl group.
- a bridged polycyclic hydrocarbon group such as a polycyclic hydrocarbon group and an adamantanediyl group.
- a part or all of the hydrogen atoms of the divalent alicyclic hydrocarbon group may be, for example, C1-C4 linear or branched such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group And a group substituted with one or more of a cyclic alkyl group or a cyclic alkyl group having 4 to 20 carbon atoms.
- a monocyclic hydrocarbon group such as a cyclopentanediyl group or a cyclohexanediyl group, or a group in which this divalent alicyclic hydrocarbon group (monocyclic hydrocarbon group) is substituted with the above alkyl group Etc. are preferred.
- preferable examples of the acid dissociable group represented by the above formula [—C (R) 3 ] include a t-butyl group, a 1-n- (1-ethyl-1-methyl) propyl group, 1- n- (1,1-dimethyl) propyl group, 1-n- (1,1-dimethyl) butyl group, 1-n- (1,1-dimethyl) pentyl group, 1- (1,1-diethyl) propyl group Group, 1-n- (1,1-diethyl) butyl group, 1-n- (1,1-diethyl) pentyl group, 1- (1-methyl) cyclopentyl group, 1- (1-ethyl) cyclopentyl group, 1- (1-n-propyl) cyclopentyl group, 1- (1-i-propyl) cyclopentyl group, 1- (1-methyl) cyclohexyl group, 1- (1-ethyl) cyclohexyl group, 1- (1-e
- the group represented by the above [—C (R) 3 ], t-butoxycarbonyl group, alkoxy-substituted methyl group and the like are preferable.
- a t-butoxycarbonyl group and an alkoxy-substituted methyl group are preferable.
- an alkoxy-substituted methyl group and a group represented by [—C (R) 3 ] are preferable.
- Alkali dissociable group refers to a group that replaces a hydrogen atom in a polar functional group such as a hydroxyl group or a carboxyl group and dissociates in the presence of an alkali.
- the alkali-dissociable group represented by R 8 and R 10 is not particularly limited as long as it exhibits the above properties, but in the general formula (2-2), it is represented by the following formula (R2-1). Can be mentioned.
- R 21 is a hydrocarbon group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.
- R 21 the description of Rf 1 described above can be applied.
- R 21 is preferably a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms in which all of the hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms, and particularly preferably a trifluoromethyl group.
- alkali dissociable group examples include groups represented by the following formulas (R2-2) to (R2-4) in the above formula (2-3).
- R 22 represents an alkyl group having a halogen atom, or 1 to 10 carbon atoms, an alkoxy group, an acyl group, or an acyloxy group.
- m 1 is an integer of 0 to 5.
- m 2 is an integer of 0-4.
- R 23 and R 24 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, or R 23 and R 24 are bonded to each other to form 4 to 20 carbon atoms.
- the alicyclic structure may be formed.
- examples of the halogen atom represented by R 10 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, fluorine atoms are preferred.
- examples of the alkyl group having 1 to 10 carbon atoms represented by R 23 or R 24 include the same groups as those described above for R 22 .
- R 23 and R 24 are bonded to each other and the alicyclic structure formed together with the carbon atoms to which they are bonded includes cyclopentane structure, methylcyclopentane structure, ethylcyclopentane structure, cyclohexane structure, methylcyclohexane structure, ethyl Examples thereof include a cyclohexane structure, an ethylcyclohexane structure, a cycloheptane structure, a methylcycloheptane structure, an ethylcycloheptane structure, and a norbornane structure.
- Specific examples of the compound represented by the above formula (R2-4) include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, a 2-butyl group, a 1-pentyl group, 2- Pentyl group, 3-pentyl group, 1- (2-methylbutyl) group, 1- (3-methylbutyl) group, 2- (3-methylbutyl) group, neopentyl group, 1-hexyl group, 2-hexyl group, 3- Hexyl group, 1- (2-methylpentyl) group, 1- (3-methylpentyl) group, 1- (4-methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methylpentyl) ) Group, 3- (2-methylpentyl) group and the like.
- the affinity of the polymer [A] to the developer may be improved. It is preferable in that it can be performed. This is presumably because the [A] polymer reacts with the developer to generate a polar group in the development step of the pattern forming method described later.
- R 7 is a (g + 1) -valent linking group.
- a linking group include a single bond or a (g + 1) -valent hydrocarbon group having 1 to 30 carbon atoms.
- a group obtained by combining these hydrocarbon groups with an oxygen atom, a sulfur atom, an imino group, a carbonyl group, —CO—O—, or —CO—NH— can be given.
- g is an integer of 1 to 3.
- g is 2 or 3, in the above formula (2-2)
- R 7 having a chain structure examples include carbon numbers such as methane, ethane, propane, butane, 2-methylpropane, pentane, 2-methylbutane, 2,2-dimethylpropane, hexane, heptane, octane, nonane and decane.
- R 7 having a cyclic structure examples include cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, and tricyclo [5.2.1.0 2,6 ].
- examples of the group in which the hydrocarbon group is combined with an oxygen atom, a sulfur atom, an imino group, a carbonyl group, —CO—O—, or —CO—NH— include groups represented by the following formulae: Can do.
- R 25 and R 26 are each independently a single bond, a divalent chain hydrocarbon group having 1 to 10 carbon atoms, a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms, or a carbon number of 6 30 to a divalent aromatic hydrocarbon group.
- g has the same meaning as in the above formula (2-2).
- R 25 and R 26 As the hydrogen group, the above description of R 7 can be applied as it is.
- R 7 may have a substituent.
- substituents include examples of the substituent that R 4 and R 6 in the above formulas (1-1) and (1-2) may have.
- Rf 2 to Rf 5 are each independently a hydrogen atom, a fluorine atom or a fluorinated hydrocarbon group having 1 to 30 carbon atoms.
- Rf 2 and Rf 3 are not both hydrogen atoms
- Rf 4 and Rf 5 are not both hydrogen atoms.
- the fluorinated hydrocarbon group having 1 to 30 carbon atoms represented by Rf 2 to Rf 5 the description of Rf 1 in the above formula (2-1) can be applied as it is.
- Examples of the partial structure represented by the following formula (b1) in the above formula (2-2) and the partial structure represented by (b2) in (2-3) include, for example, the following formulas (b-1) to ( Examples thereof include those represented by b-5).
- Examples thereof include those represented by b-5 examples thereof include those represented by b-5.
- those represented by the following formula (b-5) are preferable
- those represented by the following formula (b-3) are preferable. preferable.
- structural unit (II-2) include those represented by the following formulas (2-2-1) and (2-2-2).
- R 1 , R 7 , R 8 and g are as defined in the above formula (2-2).
- Examples of the monomer that gives such a structural unit include those represented by the following formula.
- R 1 and R 8 have the same meaning as in the above formula (2-2).
- the monomer in which R 8 is an acid-dissociable group or an alkali-dissociable group can be synthesized using, for example, a compound in which R 8 is a hydrogen atom in the above formulas as a raw material.
- a compound in which R 8 is represented by the above formula (R2-1) can be synthesized by fluoroacylating a compound in which R 8 is a hydrogen atom in each of the above formulas by a conventionally known method. .
- R 1 , R 9 and R 10 are as defined in the above formula (2-3).
- Examples of the monomer that gives such a structural unit include those represented by the following formula.
- R 1 and R 10 are as defined in the above formula (2-3).
- the monomer in which R 10 is an acid-dissociable group or an alkali-dissociable group can be synthesized using, for example, a compound or a derivative thereof in which R 10 is a hydrogen atom in the above formulas.
- R 10 when R 10 is represented by the compounds represented by the above formulas (2-2) to (2-4), these compounds include, for example, compounds represented by the following formula (m-2-3): It can be obtained by reacting with compounds represented by the following formulas (m-2-4-1) to (m-2-4-3).
- R 1 , R 9 , Rf 4 and Rf 5 are as defined in the above formula (2-3).
- R 17 represents a hydroxyl group or a halogen atom.
- R 12 has the same meaning as in formula (R2-2).
- X 1 is a halogen atom, preferably a chlorine atom.
- m1 is an integer of 0 to 5.
- X 2 is a halogen atom, preferably a bromine atom.
- m2 is an integer of 0-4.
- the monomer in which R 10 is an acid-dissociable group or an alkali-dissociable group is represented by a compound represented by the following formula (m-2-5) and a following formula (m-2-6). It can also be obtained by reacting with a compound.
- R 7 , R 10 , Rf 4 and Rf 5 are as defined in the formula (2-3).
- R 1 has the same meaning as in the formula (2-3).
- X 3 is a hydroxyl group or a halogen atom.
- the polymer may contain only one type of the structural units (II-1) to (II-3), or may contain two or more types of structural units (II-1). ) To (II-3) are preferably contained, and it is particularly preferable to combine the structural unit (II-2) and the structural unit (II-3).
- the polymer is also referred to as a structural unit having an acid-dissociable group other than the structural unit (I) in addition to the structural units (I) and (II) (hereinafter also referred to as “structural unit (III)”).
- structural unit (III) A structural unit having an alkali-soluble group (excluding those corresponding to the structural unit (II-3)) (hereinafter also referred to as “structural unit (IV)”), or a structural unit having an alkali-reactive group (Excluding those corresponding to the structural unit (II-3) above) (hereinafter also referred to as “structural unit (V)”) is preferably included.
- the structural unit (III) is a structural unit having an acid dissociable group other than the structural unit (I).
- the polymer having the structural unit (III) can adjust the solubility in the developer after exposure.
- a structural unit represented by the following formula (3) is preferable.
- R 1 is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group.
- R 31 to R 33 each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a group derived therefrom. It is.
- R 31 and R 32 are bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom formed together with the carbon atom to which each is bonded, and R 23 may be a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a group derived therefrom.
- R 23 may be a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a group derived therefrom.
- those corresponding to the above formula (1-1) or (1-2) are excluded from the above formula (3).
- R 1 examples of R 1 in the above formula (1-1) and (1-2).
- Examples of the alkyl group having 1 to 4 carbon atoms represented by R 31 to R 33 include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, Examples thereof include a 1-methylpropyl group and a t-butyl group.
- the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R 31 to R 33 , R 31 and R 32 are bonded to each other and formed together with the carbon atoms to which they are bonded.
- Examples of the divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms include a bridged skeleton such as an adamantane skeleton, a norbornane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, cyclobutane, cyclopentane, cyclohexane, Groups having a cycloalkane skeleton such as cycloheptane and cyclooctane; some or all of the hydrogen atoms of these groups are, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, 1 of a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms having 1 to 10 carbon atoms such as 2-methylpropyl group, 1-methylpropyl group and t-butyl group Or substituted group and the like with one or more.
- the monomer that gives the structural unit represented by the formula (3) include (meth) acrylic acid 2-methyladamantan-2-yl ester, (meth) acrylic acid 2-methyl-3-hydroxy.
- Adamantane-2-yl ester (meth) acrylic acid 2-ethyladamantan-2-yl ester, (meth) acrylic acid 2-ethyl-3-hydroxyadamantan-2-yl ester, (meth) acrylic acid 2-n- Propyladamantan-2-yl ester, (meth) acrylic acid 2-isopropyladamantan-2-yl ester, (meth) acrylic acid-2-methylbicyclo [2.2.1] hept-2-yl ester, (meth) Acrylic acid-2-ethylbicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid-2-ethylbicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid-8-methyltricyclo [ .2.1.0 2,6] decan-8
- the structural unit (IV) is a structural unit having an alkali-soluble group (except for those corresponding to the structural unit (II-3)). [A] Since the polymer has the structural unit (IV), the solubility in the developer after exposure is improved. As a result, the MEEF performance of the radiation sensitive resin composition and the defect suppression properties such as bridges are improved.
- the alkali-soluble group in the structural unit (IV) is preferably a functional group having a hydrogen atom having a pKa of 4 to 11 from the viewpoint of improving solubility in a developer.
- a functional group include functional groups represented by the above formulas (4-1) and (4-2).
- R 41 is a hydrocarbon group having 1 to 10 carbon atoms substituted with a fluorine atom.
- the hydrocarbon group having 1 to 10 carbon atoms substituted with a fluorine atom represented by R 41 is one in which one or more hydrogen atoms in the hydrocarbon group having 1 to 10 carbon atoms are substituted with fluorine atoms If it is, it will not specifically limit, However, A trifluoromethyl group is preferable.
- the main chain skeleton of the structural unit (IV) is not particularly limited, but is preferably a skeleton derived from a methacrylic acid ester, an acrylic acid ester, an ⁇ -trifluoroacrylic acid ester, or the like.
- Examples of the structural unit (IV) include structural units derived from monomers represented by the following formula (m-4-1) and the following formula (m-4-2), respectively.
- R 1 is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group.
- R42 is a divalent linking group.
- R 41 has the same meaning as in the formula (4-1).
- the polymer may have the structural unit (IV) singly or in combination of two or more.
- the structural unit (V) is a structural unit having an alkali-reactive group (except for those corresponding to the structural unit (II-3)).
- the alkali-reactive group in the structural unit (V) is preferably a group having a lactone structure or a cyclic carbonate structure.
- the main chain skeleton of the structural unit (V) is not particularly limited, but is preferably a skeleton derived from a methacrylic acid ester, an acrylic acid ester, an ⁇ -trifluoroacrylic acid ester, or the like.
- the structural unit (V-1) is a structural unit in which the alkali reactive group of the structural unit (V) is a group having a lactone structure.
- Examples of the structural unit (V-1) include structural units represented by the following formulas (5a-1) to (5a-6).
- R 1 is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group.
- R 51 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent.
- R 52 is a hydrogen atom or a methoxy group.
- A is a single bond, an ether group, an ester group, a carbonyl group, a divalent chain hydrocarbon group having 1 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, or a carbon number of 6 30 to 30 divalent aromatic hydrocarbon groups or a combination thereof.
- B is an oxygen atom or a methylene group.
- p is an integer of 1 to 3.
- m is 0 or 1.
- Examples of the alkyl group having 1 to 4 carbon atoms represented by R 51 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 propyl group and a t-butyl group.
- Specific examples of the substituent for substituting part or all of the hydrogen atoms of the alkyl group include halogen atoms such as fluorine atom, chlorine atom and bromine atom, phenyl group, acyloxy group and alkoxy group. It is done.
- Examples of the divalent chain hydrocarbon group having 1 to 30 carbon atoms represented by A include, for example, a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a tetramethylene group, and a pentamethylene group.
- Examples of the divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms represented by A include 1,3-cyclobutylene group, 1,3-cyclopentylene group, 1,4-cyclohexylene.
- Groups, monocyclic cycloalkylene groups such as 1,5-cyclooctylene groups; 1,4-norbornylene groups, 2,5-norbornylene groups, 1,5-adamantylene groups, 2,6-adamantylene groups, etc.
- Examples include polycyclic cycloalkylene groups.
- Examples of the divalent aromatic hydrocarbon group having 6 to 30 carbon atoms represented by A include arylene groups such as a phenylene group, a tolylene group, a naphthylene group, a phenanthrylene group, and an anthrylene group. .
- these chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups may further have a substituent.
- substituents include those that may be possessed by R 4 and R 6 in the above formulas (1-1) and (1-2).
- Preferred examples of the monomer providing the structural unit (V-1) having a lactone structure (meth) acrylic acid 5-oxo-4-oxa - tricyclo [4.2.1.0 3, 7 ] Non-2-yl ester, (meth) acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 3,7 ] non-2-yl ester, (meth) Acrylic acid-5-oxo-4-oxa-tricyclo [5.2.1.0 3,8 ] dec-2-yl ester, (meth) acrylic acid-10-methoxycarbonyl-5-oxo-4-oxa- Tricyclo [5.2.1.0 3,8 ] non-2-yl ester, (meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2.1] oct-2-yl ester, ( (Meth) acrylic acid-4-metho Cycarbonyl-6-oxo-7-oxa-bicyclo [3.2.1] oc
- the structural unit (V-2) is a structural unit in which the alkali reactive group of the structural unit (V) is a group having a cyclic carbonate structure.
- Examples of the structural unit (V-2) include a structural unit represented by the following formula (5b).
- R 1 is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group.
- R 53 is a hydrogen atom or a chain hydrocarbon group having 1 to 5 carbon atoms.
- n is an integer of 2 to 4.
- D is a single bond, a divalent or trivalent chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group that may contain a divalent or trivalent heteroatom having 3 to 30 carbon atoms, Or a divalent or trivalent aromatic hydrocarbon group having 6 to 30 carbon atoms.
- D is a trivalent hydrocarbon group, the carbon atom contained in D and the carbon atom constituting the cyclic carbonate ring are bonded to form a ring structure.
- D may contain a single bond, a divalent or trivalent chain hydrocarbon group having 1 to 30 carbon atoms, or a divalent or trivalent heteroatom having 3 to 30 carbon atoms.
- Particularly preferred examples of the structural unit represented by the above formula (5b) include structural units represented by the following formulas (5b-1) to (5b-21).
- R 1 has the same meaning as in the above formula (5b).
- the polymer comprises, as the structural unit (V), a structural unit represented by the above formulas (5a-1) to (5a-6) and a structural unit represented by the above formula (5b-1).
- the inclusion of at least one structural unit selected from the group is particularly preferred from the viewpoint of improving solubility in a developer.
- the polymer may contain only one type of structural unit (V), or may contain two or more types.
- the content ratio of the structural unit (I) is preferably 10 to 90 mol%, more preferably 20 to 90 mol% from the viewpoint of further improving the MEEF performance and the defect suppressing properties such as bridges of the radiation sensitive resin composition. 80 mol%, more preferably 30 to 80 mol%.
- the content ratio of the structural unit (II) is from the viewpoint of more efficiently increasing the elution control of the acid generator from the resist film to the immersion exposure liquid and the receding contact angle between the resist film and the immersion exposure liquid.
- the content is preferably 20 to 90 mol%, more preferably 20 to 80 mol%, still more preferably 20 to 70 mol%.
- the content ratio of the structural unit (III) is usually 80 mol% or less, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, from the viewpoint of further improving the pattern formability.
- the content ratio of the structural unit (IV) is usually 50 mol% or less, preferably 5 to 30 mol%, from the viewpoint of further improving the MEEF performance of the radiation-sensitive resin composition and the defect suppressing properties such as bridges. Preferably, it is 5 to 20 mol%.
- the content of the structural unit (V) is usually 50 mol% or less, preferably 5 to 30 mol%, from the viewpoint of improving the affinity of the resist film formed from the radiation-sensitive resin composition to the developer. Preferably, it is 5 to 20 mol%.
- the fluorine atom content in the polymer is 5% by mass or more, preferably 5 to 50% by mass, more preferably 5 to 40% by mass, based on 100% by mass of the entire [A] polymer.
- the fluorine atom content can be measured by 13 C-NMR.
- the repellency of the resist coating surface formed by the radiation sensitive resin composition containing the [A] polymer and the [B] polymer to be described later is included.
- the aqueous property can be increased, and it is not necessary to separately form an upper layer film during immersion exposure.
- the content of the [A] polymer in the radiation sensitive resin composition is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 100 parts by mass of the polymer [B] described later. Is 0.5 parts by mass or more and 15 parts by mass or less. By making this content within the above range, it is possible to further suppress bridge defects and to form a pattern that is further excellent in MEEF performance. In addition, it is possible to obtain a resist film in which acid generators and the like are more difficult to elute. [A] When the content of the polymer is smaller than the lower limit, the effect tends to be small. On the other hand, if the content of [A] polymer is larger than the above upper limit, when a line-and-space pattern is formed, the depth of focus of an isolated line (line part) becomes small or development defects occur. There is a fear.
- the polymer may be contained in the radiation-sensitive resin composition of the present invention only in one kind, or in two or more kinds.
- a polymerizable unsaturated monomer that gives each predetermined structural unit is used as a radical polymerization initiator such as hydroperoxides, dialkyl peroxides, diacyl peroxides, and azo compounds. And it can synthesize
- Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; cyclohexane, cycloheptane, cyclooctane, decalin, Cycloalkanes such as norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene; ethyl acetate Saturated carboxylic acid esters such as n-butyl acetate, i-butyl acetate and methyl propionate; ketones such as acetone, 2-butanone, 4-methyl-2-pent
- the reaction temperature in the polymerization is preferably 40 to 150 ° C, more preferably 50 to 120 ° C.
- the reaction time is preferably 1 to 48 hours, more preferably 1 to 24 hours.
- the weight average molecular weight (hereinafter also referred to as “Mw”) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is preferably 1,000 to 50,000, more preferably 1, 000 to 40,000, more preferably 1,000 to 30,000.
- Mw weight average molecular weight
- GPC gel permeation chromatography
- the ratio (Mw / Mn) of the polymer Mw to the polystyrene-equivalent number average molecular weight (hereinafter also referred to as “Mn”) by GPC is preferably 1 to 5, more preferably 1 to 4. It is.
- the polymer is more preferable as the content of impurities such as halogen and metal is smaller.
- the content of impurities is small, the sensitivity, resolution, process stability, pattern shape and the like of the resist film can be further improved.
- Polymer purification methods include, for example, chemical purification methods such as water washing and liquid-liquid extraction, and combinations of these chemical purification methods and physical purification methods such as ultrafiltration and centrifugation.
- Etc examples of the solvent used for liquid-liquid extraction include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; methanol, ethanol, 1-propanol, 2-propanol And alcohols such as 4-methyl-2-pentanol; ketones such as acetone, 2-butanone, 4-methyl-2-pentanone and 2-heptanone.
- n-hexane, n-heptane, methanol, ethanol, acetone, and 2-butanone are preferable.
- the polymer is a polymer having an acid dissociable group and a fluorine atom content of less than 5% by mass.
- the polymer becomes alkali-soluble when the acid-dissociable group is dissociated.
- the acid dissociable group of the polymer is not particularly limited, but is preferably a group having a cyclic hydrocarbon group in its structure.
- the [B] polymer containing an acid-dissociable group having a cyclic hydrocarbon group has an advantage that the sensitivity is increased because the acid-dissociable group is easily dissociated.
- Examples of the acid-dissociable group having a cyclic hydrocarbon include 1- (1-methyl) cyclopentyl group, 1- (1-ethyl) cyclopentyl group, 1- (1-n-propyl) cyclopentyl group, 1- ( 1-isopropyl) cyclopentyl group, 1- (1-methyl) cyclohexyl group, 1- (1-ethyl) cyclohexyl group, 1- (1-methyl) cyclooctyl group, 1- (1-ethyl) cyclooctyl group, 1 Examples include-(1-methyl) adamantyl group, 1- (1-ethyl) adamantyl group, 1- (1-n-propyl) adamantyl group and 1- (1-isopropyl) adamantyl group.
- some or all of the hydrogen atoms in these groups may be, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-methylpropyl, 2-methylpropyl, Examples thereof include a group substituted with one or more linear alkyl groups having 1 to 4 carbon atoms, such as a t-butyl group, branched or cyclic alkyl groups having 4 to 20 carbon atoms.
- 1- (1-ethyl) cyclopentyl group is preferable from the viewpoint of easy dissociation of the acid dissociable group.
- polymer specifically, a polymer having an alicyclic skeleton such as a norbornane ring obtained by polymerizing a norbornene derivative or the like, a copolymer of norbornene derivative and maleic anhydride is copolymerized.
- the polymer preferably contains the structural unit (I) and / or the structural unit (III) (hereinafter collectively referred to as “structural unit (b1)”).
- the content of the structural unit (b1) in the polymer is preferably 10 to 70 mol%, more preferably 15 to 60 mol%, based on all structural units constituting the [B] polymer. %, More preferably 20 to 50 mol%. If this content is less than the lower limit, the resolution of the formed resist film may be reduced. On the other hand, if this content ratio is larger than the above upper limit, the developability and the exposure margin may be reduced.
- the polymer is also referred to as a structural unit having a lactone structure (hereinafter also referred to as “lactone structure-containing structural unit”) or a structural unit containing a cyclic carbonate structure (hereinafter referred to as “cyclic carbonate structure-containing structural unit”). ).
- lactone structure-containing structural unit a structural unit having a lactone structure
- cyclic carbonate structure-containing structural unit a structural unit containing a cyclic carbonate structure
- the content ratio of the lactone structure-containing structural unit and the cyclic carbonate structure-containing structural unit in the polymer is 5 to 85 mol% with respect to all the structural units constituting the [B] polymer. It is preferably 10 to 70 mol%, more preferably 15 to 60 mol%.
- the fluorine atom content in the polymer is less than 5% by mass, preferably 0 to 4.9% by mass, more preferably 0 to 4% by mass.
- the fluorine atom content can be measured by 13 C-NMR.
- the fluorine atom content in the polymer is within the above range, the surface of the resist coating formed by the radiation sensitive resin composition containing the [B] polymer and the above-mentioned [A] polymer is repelled.
- the aqueous property can be increased, and it is not necessary to separately form an upper layer film during immersion exposure.
- a polymerizable unsaturated monomer that gives each predetermined structural unit is used as a radical polymerization initiator such as hydroperoxides, dialkyl peroxides, diacyl peroxides, and azo compounds. And it can synthesize
- Examples of the solvent used for the polymerization of the above [B] polymer include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; cyclohexane, cycloheptane , Cycloalkanes such as cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; halogenation of chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene, etc.
- alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane
- Hydrocarbons saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; ketones such as acetone, 2-butanone, 4-methyl-2-pentanone and 2-heptanone; Tetrahydrofuran, dimethoxyethanes, diethoxyethanes, etc. It can be mentioned ethers. These solvents may be used alone or in combination of two or more.
- the reaction temperature in the polymerization is preferably 40 to 150 ° C, more preferably 50 to 120 ° C.
- the reaction time is preferably 1 to 48 hours, more preferably 1 to 24 hours.
- the Mw by GPC of the polymer is preferably 1,000 to 100,000, more preferably 1,000 to 30,000, and still more preferably 1,000 to 20,000. If this Mw is less than the above lower limit, the heat resistance of the formed resist film may be reduced. On the other hand, if this Mw exceeds the above upper limit, the developability of the formed resist film may be lowered.
- the ratio of Mw to Mn (Mw / Mn) of the polymer is preferably 1 to 5, more preferably 1 to 3.
- the content ratio of the low molecular weight component (hereinafter also referred to as “low molecular weight component (b)”) derived from the monomer used when preparing the [B] polymer is 0% in the [B] polymer. It is preferably 1% by mass or less, more preferably 0.07% by mass or less, and still more preferably 0.05% by mass or less. When this content is 0.1% by mass or less, it is possible to reduce the amount of the eluate that is eluted with respect to the immersion exposure liquid such as water in contact with the resist film during the immersion exposure. Furthermore, in addition to the occurrence of foreign matters during storage of the radiation-sensitive resin composition and the occurrence of coating unevenness during application, the occurrence of defects during resist pattern formation can be further suppressed.
- the low molecular weight component (b) is a component having a molecular weight of 500 or less, and examples thereof include a monomer, a dimer derived from the monomer, a trimer, and an oligomer.
- the low molecular weight component (b) is, for example, a chemical purification method such as washing with water, liquid-liquid extraction, or a combination of these chemical purification methods and a physical purification method such as ultrafiltration or centrifugation. Can be removed.
- the [B] polymer is more preferable as the content of impurities such as halogen and metal is smaller.
- the content of such impurities is small, the sensitivity, resolution, process stability, pattern shape and the like of the resist film can be further improved.
- the polymer may be contained in the radiation-sensitive resin composition of the present invention only in one kind, or in two or more kinds.
- the acid generator generates an acid upon exposure.
- the acid generator dissociates the acid-dissociable group present in the [A] polymer by the action of the acid generated by exposure, and makes the [A] polymer alkali-soluble. As a result, the exposed portion of the resist film becomes readily soluble in an alkali developer, and a positive resist pattern can be formed.
- Examples of the [C] acid generator include compounds described in paragraphs [0080] to [0113] of JP-A-2009-134088.
- the acid generator include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, and bis (4-t-butylphenyl) iodonium.
- Trifluoromethanesulfonate bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium Nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, cyclohexyl-2-oxocyclohexane Sill - methyl trifluoromethanesulfonate, dicyclohexyl-2-oxo-cyclohexyl trifluoromethane sulfonate, 2-oxo-cyclohexyl dimethyl sulfonium trifluoromethane sulfonate, 4-hydroxy-1-
- Trifluoromethanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide Perfluoro-n-octanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide nonafluoro-n-butanesulfonate, N -Hydroxysuccinimide perfluoro-n-octane sulfonate and 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate are preferred.
- the acid generator can be contained singly or in combination of two or more.
- the content of the acid generator is preferably 0.1 to 30 parts by mass, more preferably 2 to 27 parts by mass with respect to 100 parts by mass of the [A] polymer. Particularly preferred is 25 parts by mass.
- the content of the acid generator is less than 0.1 parts by mass, the sensitivity and resolution as a resist film may be lowered.
- the content of the [C] acid generator exceeds 30 parts by mass, applicability as a resist film and pattern shape may be deteriorated.
- the radiation sensitive resin composition of the present invention includes an acid diffusion controller, a solvent, and various additives as necessary.
- Arbitrary components such as (for example, an alicyclic additive, surfactant, a lactone compound, etc.), can be contained.
- Examples of the acid diffusion controller include a compound represented by the following formula (6) (hereinafter, also referred to as “nitrogen-containing compound (I)”), a compound having two nitrogen atoms in the same molecule (hereinafter, “ Nitrogen-containing compound (II) “), compounds having 3 or more nitrogen atoms (hereinafter also referred to as” nitrogen-containing compound (III) "), amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc. Can be mentioned.
- the radiation-sensitive resin composition can improve the good pattern shape and dimensional fidelity as a resist by containing an acid diffusion controller.
- R 61 to R 63 are each independently a hydrogen atom, or a linear, branched or cyclic alkyl group, aryl group or aralkyl group which may be substituted.
- nitrogen-containing compound (I) examples include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; di-n-butylamine, di-n- Dialkylamines such as pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine; triethylamine, tri-n-propylamine, Trialkylamines such as tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine Aniline, N-methylaniline, N, N-dimethylaniline,
- nitrogen-containing compound (II) examples include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, tetramethylenediamine, Hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2′-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- ( 4-aminophenyl) -1-methylethyl] benzene and the like.
- nitrogen-containing compound (III) examples include polymers of polyethyleneimine, polyallylamine, dimethylaminoethylacrylamide, and the like.
- amide group-containing compounds include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like. Can be mentioned.
- urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tributylthiourea and the like. Can do.
- nitrogen-containing heterocyclic compound examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, and N-methyl-4-phenylpyridine.
- pyridines such as nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxyquinoline, acridine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1, Examples include 4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, and the like.
- nitrogen-containing compounds (I), nitrogen-containing compounds (II), and nitrogen-containing heterocyclic compounds are preferable.
- the acid diffusion controller can be used alone or in combination of two or more.
- the content of the acid diffusion controller is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less with respect to 100 parts by mass of the [B] polymer. When the content of the acid diffusion controller exceeds the above upper limit, the sensitivity of the formed resist film tends to be remarkably lowered.
- An alicyclic additive is a component that exhibits an action of further improving dry etching resistance, pattern shape, adhesion to a substrate, and the like.
- Examples of such alicyclic additives include t-butyl 1-adamantanecarboxylate, t-butoxycarbonylmethyl 1-adamantanecarboxylate, di-t-butyl 1,3-adamantanedicarboxylate, and 1-adamantyl acetic acid.
- adamantane derivatives such as t-butyl, 1-adamantyl acetate t-butoxycarbonylmethyl, 1,3-adamantylene diacetate di-t-butyl; deoxycholate t-butyl, deoxycholate t-butoxycarbonylmethyl, deoxy Deoxycholic acid esters such as 2-ethoxyethyl cholic acid, 2-cyclohexyloxyethyl deoxycholic acid, 3-oxocyclohexyl deoxycholic acid, tetrahydropyranyl deoxycholic acid, mevalonolactone ester deoxycholic acid; lithocholic acid t- Butyl, Lithocholic acid esters such as t-butoxycarbonylmethyl tocholate, 2-ethoxyethyl lithocholic acid, 2-cyclohexyloxyethyl lithocholic acid, 3-oxocyclohexyl lithocholic acid, tetrahydropyranyl lit
- alicyclic additives can be used individually by 1 type or in mixture of 2 or more types. Content of an alicyclic additive is 50 mass parts or less normally with respect to 100 mass parts of [B] polymers, Preferably it is 30 mass parts or less.
- a surfactant is a component that exhibits an effect of improving coatability, developability, and the like.
- examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate.
- nonionic surfactants such as polyethylene glycol distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no.
- the lactone compound has an effect of efficiently segregating the [A] polymer on the resist film surface. Therefore, the amount of the [A] polymer added can be made smaller than before by containing this lactone compound. Therefore, the elution of components from the resist film to the immersion liquid can be suppressed without impairing the basic characteristics of the resist such as LWR (Line Width Roughness) goodness, development defect suppression, and pattern collapse resistance, and high speed in immersion exposure. Even in scanning, the remaining of the droplets is suppressed, and as a result, it is possible to suppress defects caused by immersion exposure such as watermark defects while maintaining the water repellency of the resist film surface.
- LWR Line Width Roughness
- lactone compound examples include ⁇ -butyrolactone, valerolactone, mevalonic lactone, norbornane lactone, and the like.
- the radiation-sensitive resin composition may contain only one type of the lactone compound or two or more types.
- the content of the lactone compound is preferably 30 to 200 parts by mass, more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the [B] polymer.
- the said radiation sensitive resin composition can be prepared by mixing a [A] polymer, a [B] polymer, a [C] acid generator, and an arbitrary component as needed in a predetermined ratio, for example.
- the radiation-sensitive resin composition is usually dissolved in a solvent so that the total solid content concentration is 1 to 50% by mass, preferably 3 to 25% by mass, and then, for example, the pore size is about 0.02 ⁇ m. It is prepared as a composition solution by filtering with a filter.
- solvent used for the preparation of the composition solution examples include linear or branched ketones; cyclic ketones; propylene glycol monoalkyl ether acetates; alkyl 2-hydroxypropionate; 3-alkoxypropion.
- alkyl acids linear or branched ketones
- cyclic ketones propylene glycol monoalkyl ether acetates
- alkyl 2-hydroxypropionate 3-alkoxypropion.
- n-propyl alcohol i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether , Propylene glycol monoethyl Ether, propylene glycol mono -n- propyl ether,
- solvents can be used singly or in combination of two or more.
- linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, alkyl 2-hydroxypropionate, and alkyl 3-alkoxypropionate are preferable.
- the resist pattern forming method of the present invention includes (1) a step of forming a photoresist film on a substrate using the radiation-sensitive resin composition (hereinafter also referred to as “step (1)”), (2). A step of placing an immersion exposure liquid on the photoresist film, and subjecting the photoresist film to immersion exposure via the immersion exposure liquid (hereinafter also referred to as “step (2)”); 3) A step of developing the photoresist film subjected to immersion exposure to form a resist pattern (hereinafter also referred to as “step (3)”). According to the resist pattern forming method, a resist pattern having a good pattern shape can be formed.
- the radiation-sensitive resin composition of the present invention is applied onto a substrate such as a silicon wafer or a wafer coated with aluminum by an appropriate application means such as spin coating, cast coating or roll coating.
- a resist film is formed.
- the solvent in the coating film is volatilized by pre-baking (PB) to form a resist film. Is done.
- the thickness of the resist film is not particularly limited, but is preferably 10 to 5,000 nm, and more preferably 10 to 2,000 nm.
- the prebaking heating conditions vary depending on the composition of the radiation sensitive resin composition, but are preferably about 30 to 200 ° C, more preferably 50 to 150 ° C.
- an immersion exposure liquid is disposed on the photoresist film formed in the step (1), and radiation is irradiated through the immersion exposure liquid to expose the photoresist film by immersion exposure.
- immersion exposure liquid for example, pure water, a long chain or cyclic aliphatic compound, or the like can be used.
- the radiation is appropriately selected from visible rays, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, etc., depending on the type of [C] acid generator used.
- ArF excimer laser (wavelength 193 nm) or far ultraviolet rays represented by KrF excimer laser (wavelength 248 nm) are preferable, and ArF excimer laser (wavelength 193 nm) is particularly preferable.
- the exposure conditions such as the exposure amount can be appropriately selected according to the blending composition of the radiation-sensitive resin composition, the kind of additive, and the like.
- PEB post-exposure baking
- the heating condition of PEB is appropriately adjusted depending on the composition of the radiation sensitive resin composition, but is usually 30 to 200 ° C., preferably 50 to 170 ° C.
- the pattern forming method of the present invention is disclosed in, for example, Japanese Patent Publication No. 6-12452 (Japanese Patent Laid-Open No. 59-93448) and the like in order to maximize the potential of the radiation-sensitive resin composition.
- an organic or inorganic antireflection film can be formed on the substrate to be used.
- a protective film can be provided on the resist film as disclosed in, for example, Japanese Patent Laid-Open No. 5-188598.
- an immersion protective film is provided on the resist film as disclosed in, for example, Japanese Patent Application Laid-Open No. 2005-352384. You can also. Moreover, these techniques can be used together.
- a resist pattern can be formed.
- the protective film (upper layer film) forming step can be omitted, and an improvement in throughput can be expected.
- step (3) a predetermined resist pattern is formed by developing the resist film subjected to the immersion exposure in step (2).
- Examples of the developer used for the development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, and di-n-propyl.
- Amine triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo
- An alkaline aqueous solution in which at least one alkaline compound such as [4.3.0] -5-nonene is dissolved is preferable.
- the concentration of the alkaline aqueous solution is preferably 10% by mass or less. When the concentration of the alkaline aqueous solution exceeds 10% by mass, the unexposed area may be dissolved in the developer.
- An organic solvent can also be added to the developer composed of the alkaline aqueous solution.
- the organic solvent include ketones such as acetone, 2-butanone, methyl i-butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethylcyclohexanone; methyl alcohol, ethyl alcohol, n Alcohols such as -propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1,4-hexanedimethylol; tetrahydrofuran, dioxane, etc.
- ketones such as acetone, 2-butanone, methyl i-butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethyl
- Ethers such as ethyl acetate, n-butyl acetate, and i-amyl acetate; aromatic hydrocarbons such as toluene and xylene; phenol, acetonyl acetone, dimethylformamide, and the like.
- organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type.
- the amount of the organic solvent used is preferably 100 parts by volume or less with respect to 100 parts by volume of the alkaline aqueous solution. If the amount of the organic solvent used exceeds 100 parts by volume, the developability is lowered, and there is a possibility that the development residue in the exposed part increases.
- An appropriate amount of a surfactant or the like can be added to the developer composed of the alkaline aqueous solution.
- After developing with the developing solution which consists of alkaline aqueous solution generally it wash
- the polymer of the present invention has at least one structural unit (I) selected from the group consisting of a plurality of structural units represented by the above formulas (1-1) and (1-2). It is a polymer having an atomic content of 5% by mass or more.
- R 1 each independently represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group.
- Y is a (2 + d) -valent saturated hydrocarbon group.
- R 2 and R 3 are each independently an alkyl group. However, R 2 and R 3 may be bonded to each other to form an alicyclic structure together with Y.
- R 4 is an alkyl group, an alkoxy group, an acyl group, or an acyloxy group. When a plurality of R 3 or R 4 are present, the plurality of R 3 and R 4 may be the same or different. Some or all of the hydrogen atoms of R 4 may be substituted.
- a is 1 or 2.
- R 5 is an alkyl group.
- R 6 is an alkyl group, an alkoxy group, an acyl group, or an acyloxy group. If R 6 there are a plurality, the plurality of R 6 may be the same or different. A part or all of the hydrogen atoms of R 6 may be substituted.
- e is 1 or 2.
- f is an integer of 0 to 5.
- the polymer has a characteristic that it can be unevenly distributed in the resist film surface layer when the fluorine atom content is a predetermined value or more, and is easily dissolved in a developer after the action of an acid. is doing. Therefore, the said polymer is suitable for the radiation sensitive resin composition etc. which are used for lithography technique, for example.
- Mw and Mn of [A] polymer and [B] polymer are GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation, tetrahydrofuran is used as an elution solvent, and the flow rate is 1.0 mL / min. Measurement was performed by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under analytical conditions at a column temperature of 40 ° C. Further, the degree of dispersion (Mw / Mn) was calculated from the measurement results of Mw and Mn.
- GPC gel permeation chromatography
- polymer (A-1) The polymer in this propylene glycol monomethyl ether acetate solution is referred to as polymer (A-1).
- This polymer (A-1) had Mw of 6,000 and Mw / Mn of 1.7.
- the polymer (A-1) has a content ratio [(M-1) :( M-7) :( M-8)] of each structural unit derived from each monomer. , 58.8: 23.4: 17.8 (mol%) copolymer.
- the inside of the flask was heated to 80 ° C. with stirring, and the monomer solution was added dropwise using a dropping funnel over 3 hours.
- 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 poured into 4,000 g of methanol to precipitate a white powder. Thereafter, the precipitated white powder was filtered off. The filtered white powder was washed twice by slurrying with 800 g of methanol, and then filtered off. Then, it was dried at 50 ° C. for 17 hours to obtain a white powder polymer (B-1) (70 g, yield 70%).
- This polymer (B-1) had Mw of 4,300 and Mw / Mn of 1.3. As a result of 13 C-NMR analysis, the polymer (B-1) has a content ratio of each structural unit derived from each monomer [(MA) :( MB) :( MC) :( MD)] was a 36.8: 9.4: 10.2: 43.6 (mol%) copolymer.
- Synthesis Example 13 (Synthesis of polymer (B-2))
- Synthesis Example 12 the same manner as in Synthesis Example 12 except that a compound (monomer) having the type and mixing ratio shown in Table 3 below was used, and that 5 mol% of AIBN was used with respect to the monomer amount.
- a polymer (B-2) was synthesized.
- Table 4 shows the measured values of the content ratio, weight average molecular weight (Mw) and dispersity (Mw / Mn) of the structural units derived from the respective monomers for the polymers (B-1) and (B-2). .
- C-1) 4-cyclohexylphenyldiphenylsulfonium nonafluorobutanesulfonate (compound represented by the following formula (C-1))
- C-2) Triphenylsulfonium nonafluorobutanesulfonate (compound represented by the following formula (C-2))
- Example 1 3 parts of polymer (A-1), 100 parts of polymer (B-1), 12 parts of acid generator (C-1), 1 part of acid diffusion controller (D-1), solvent (E-1) 1 , 360 parts, solvent (E-2) 580 parts, and lactone compound (F-1) 30 parts were mixed to prepare a radiation sensitive resin composition of Example 1.
- Example 2 the radiation sensitive resin compositions of Examples 2 to 10 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1 except that the components were mixed in the types and amounts shown in Table 5 below. Prepared.
- PEB post exposure baking
- the exposure amount for forming a line-and-space pattern (1L1S) having a line width of 100 nm with a one-to-one line width was defined as the optimum exposure amount, and this optimum exposure amount was defined as the sensitivity.
- a scanning electron microscope (“S-9380”, manufactured by Hitachi High-Technologies Corporation) was used. Thereafter, the number of defects on the line and space pattern (1L1S) having a line width of 100 nm was measured using a defect inspection apparatus (“KLA2351” manufactured by KLA-Tencor).
- Eop optimum exposure amount
- the slope of the straight line when the target size (nm) was plotted on the horizontal axis and the line width (nm) formed on the resist film using each mask pattern was plotted on the vertical axis was calculated as MEEF performance.
- the MEEF performance slope of the straight line
- the mask reproducibility is better.
- the value is 1.00 ⁇ MEEF ⁇ 1.25, “good” is set, and 1.25 ⁇ MEEF ⁇ 1.
- the case of 50 was evaluated as “slightly good”, and 1.50 ⁇ MEEF was evaluated as “bad”.
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Abstract
Description
[A]下記式(1-1)及び(1-2)でそれぞれ表される複数の構造単位からなる群より選択される少なくとも1種の構造単位(I)を有し、フッ素原子含有量が5質量%以上である重合体(以下、「[A]重合体」ともいう。)、
[B]酸解離性基を有し、フッ素原子含有量が5質量%未満である重合体(以下、「[B]重合体」ともいう。)、及び
[C]感放射線性酸発生剤(以下、「[C]酸発生剤」ともいう。)
を含有する感放射線性樹脂組成物である。
式(1-1)中、Yは、(2+d)価の飽和炭化水素基である。R2及びR3は、それぞれ独立して、アルキル基である。但し、R2及びR3が互いに結合してYと共に脂環式構造を形成していてもよい。R4は、アルキル基、アルコキシ基、アシル基又はアシロキシ基である。R3又はR4が複数存在する場合、複数のR3及びR4はそれぞれ同一でも異なっていてもよい。R4の水素原子の一部又は全部が置換されていてもよい。aは、1又は2である。bは、0~3の整数である。dは、1又は2である。
式(1-2)中、R5は、アルキル基である。R6は、アルキル基、アルコキシ基、アシル基又はアシロキシ基である。R6が複数存在する場合、複数のR6は同一でも異なっていてもよい。R6の水素原子の一部又は全部が置換されていてもよい。eは1又は2である。fは0~5の整数である。)
式(2-1)中、Rf1は、炭素数1~30のフッ素化炭化水素基である。
式(2-2)中、R7は、(g+1)価の連結基である。R8は、水素原子又は1価の有機基である。R8が複数存在する場合、複数のR8は同一でも異なっていてもよい。Rf2及びRf3は、それぞれ独立して、水素原子、フッ素原子又は炭素数1~30のフッ素化炭化水素基である。但し、Rf2及びRf3の両方が共に水素原子である場合である場合はない。Rf2又はRf3が複数存在する場合、複数のRf2及びRf3はそれぞれ同一でも異なっていてもよい。gは、1~3の整数である。
式(2-3)中、R9は2価の連結基である。R10は、水素原子又は1価の有機基である。Rf4及びRf5は、それぞれ独立して、水素原子、フッ素原子又は炭素数1~30のフッ素化炭化水素基である。但し、Rf4及びRf5の両方が共に水素原子である場合である場合はない。)
下記式(1-1)及び(1-2)でそれぞれ表される複数の構造単位からなる群より選択される少なくとも1種の構造単位(I)を有し、フッ素原子含有量が5質量%以上である。
式(1-1)中、Yは、(2+d)価の飽和炭化水素基である。R2及びR3は、それぞれ独立して、アルキル基である。但し、R2及びR3が互いに結合してYと共に脂環式構造を形成していてもよい。R4は、アルキル基、アルコキシ基、アシル基又はアシロキシ基である。R3又はR4が複数存在する場合、複数のR3及びR4はそれぞれ同一でも異なっていてもよい。R4の水素原子の一部又は全部が置換されていてもよい。aは、1又は2である。bは、0~3の整数である。dは、1又は2である。
式(1-2)中、R5は、アルキル基である。R6は、アルキル基、アルコキシ基、アシル基又はアシロキシ基である。R6が複数存在する場合、複数のR6は同一でも異なっていてもよい。R6の水素原子の一部又は全部が置換されていてもよい。eは1又は2である。fは0~5の整数である。)
式(2-1)中、Rf1は、炭素数1~30のフッ素化炭化水素基である。
式(2-2)中、R7は、(g+1)価の連結基である。R8は、水素原子又は1価の有機基である。R8が複数存在する場合、複数のR8は同一でも異なっていてもよい。Rf2及びRf3は、それぞれ独立して、水素原子、フッ素原子又は炭素数1~30のフッ素化炭化水素基である。但し、Rf2及びRf3の両方が共に水素原子である場合である場合はない。Rf2又はRf3が複数存在する場合、複数のRf2及びRf3はそれぞれ同一でも異なっていてもよい。gは、1~3の整数である。
式(2-3)中、R9は2価の連結基である。R10は、水素原子又は1価の有機基である。Rf4及びRf5は、それぞれ独立して、水素原子、フッ素原子又は炭素数1~30のフッ素化炭化水素基である。但し、Rf4及びRf5の両方が共に水素原子である場合である場合はない。)
(1)当該感放射線性樹脂組成物を用いて基板上にフォトレジスト膜を形成する工程、
(2)上記フォトレジスト膜上に液浸露光用液体を配置し、この液浸露光用液体を介して上記フォトレジスト膜を液浸露光する工程、及び
(3)液浸露光された上記フォトレジスト膜を現像してレジストパターンを形成する工程
を有する。
なお、本明細書において、「(メタ)アクリル」とは、アクリル及び/又はメタクリルを意味する。
本発明の感放射線性樹脂組成物は、[A]重合体、[B]重合体及び[C]酸発生剤を含有する。また、当該感放射線性樹脂組成物は、本発明の効果を損なわない範囲において、任意成分を含有してもよい。当該感放射線性樹脂組成物は、良好なパターン形状を得ることが可能で、MEEF性能に優れ、またブリッジ欠陥等を生じ難い。以下、各構成成分について説明する。
[A]重合体は、上記式(1-1)及び(1-2)でそれぞれ表される複数の構造単位からなる群より選択される少なくとも1種の構造単位(I)を有し、フッ素原子含有量が5質量%以上の重合体である。[A]重合体は所定量以上のフッ素原子を含有するので、当該感放射線性樹脂組成物からレジスト被膜を形成した際に、被膜中の[A]重合体の撥油性的特徴により、その分布がレジスト被膜表面で高くなる傾向がある。そのため、液浸露光時において、レジスト被膜中の酸発生剤や酸拡散制御剤等が、水等の液浸露光液に溶出してしまうことを抑制することができる。一方、フッ素原子を含む重合体は一般的には現像液に対する溶解性が低い傾向にあるため、このような重合体がレジスト被膜表層に偏在することはブリッジ欠陥が発生する要因の一つであると考えられる。しかし、この[A]重合体を含有する感放射線性樹脂組成物によれば、ブリッジ等の欠陥を生じにくくなる。これは構造単位(I)の酸解離性基が酸による解離を生じやすく、その結果、露光部における[A]重合体の現像液に対する溶解性を高くすることができるためであると考えられる。
構造単位(I)は、上記式(1-1)及び(1-2)でそれぞれ表される複数の構造単位からなる群より選択される少なくとも1種の構造単位である。
上記式(1-1)中、Yは、(2+d)価の飽和炭化水素基である。R2及びR3は、それぞれ独立して、アルキル基である。但し、R2及びR3が互いに結合してYと共に脂環式構造を形成していてもよい。R4は、アルキル基、アルコキシ基、アシル基又はアシロキシ基である。R3又はR4が複数存在する場合、複数のR3及びR4はそれぞれ同一でも異なっていてもよい。R4の水素原子の一部又は全部が置換されていてもよい。aは、1又は2である。bは、0~3の整数である。dは、1又は2である。
上記式(1-2)中、R5は、アルキル基である。R6は、アルキル基、アルコキシ基、アシル基又はアシロキシ基である。R6が複数存在する場合、複数のR6は同一でも異なっていてもよい。R6の水素原子の一部又は全部が置換されていてもよい。eは1又は2である。fは0~5の整数である。
[A]重合体は、構造単位(I)以外にも、上記式(2-1)~(2-3)でそれぞれ表される複数の構造単位からなる群より選択される少なくとも1種のフッ素原子を有する構造単位(II)をさらに有していてもよい。[A]重合体が、構造単位(II)を有することで、レジスト被膜中の酸発生剤や酸拡散制御剤等の液浸露光液に対する溶出を抑制し、またレジスト被膜と液浸露光液との後退接触角の向上により、液浸露光液の液滴が、レジスト被膜上に残りにくく、その結果、液浸露光液に起因する欠陥の発生を抑制することができる。
構造単位(II-1)は、上記式(2-1)で表される構造単位である。
式(2-1)中、Rf1は、炭素数1~30のフッ素化炭化水素基である。
上記式(2-2)~(2-3)中、R1は、水素原子、低級アルキル基又はハロゲン化低級アルキル基である。
上記式(2-2)中、R7は、(g+1)価の連結基である。R8は、水素原子又は1価の有機基である。R8が複数存在する場合、複数のR8は同一でも異なっていてもよい。Rf2及びRf3は、それぞれ独立して、水素原子、フッ素原子又は炭素数1~30のフッ素化炭化水素基である。但し、Rf2及びRf3の両方が共に水素原子である場合である場合はない。Rf2又はRf3が複数存在する場合、複数のRf2及びRf3はそれぞれ同一でも異なっていてもよい。gは、1~3の整数である。
上記式(2-3)中、R9は2価の連結基である。R10は、水素原子又は1価の有機基である。Rf4及びRf5は、それぞれ独立して、水素原子、フッ素原子又は炭素数1~30のフッ素化炭化水素基である。但し、Rf4及びRf5の両方が共に水素原子である場合である場合はない。
上記式(R2-4)中、R23及びR24はそれぞれ独立して水素原子又は炭素数1~10のアルキル基であるか、又はR23及びR24が互いに結合して炭素数4~20の脂環式構造を形成してもよい。
上記式(m-2-4-1)中、X1は、ハロゲン原子であり、好ましくは塩素原子である。m1は0~5の整数である。
上記式(m-2-4-2)中、X2は、ハロゲン原子であり、好ましくは臭素原子である。m2は0~4の整数である。
上記式(m-2-6)中、R1は、式(2-3)と同義である。X3は水酸基又はハロゲン原子である。
構造単位(III)は上記構造単位(I)以外の酸解離性基を有する構造単位である。[A]重合体は、構造単位(III)を有することで、露光後における現像液への溶解性を調整することができる。構造単位(III)としては、例えば、下記式(3)で表される構造単位が好ましい。
構造単位(IV)は、アルカリ可溶性基を有する構造単位である(但し、上記構造単位(II-3)に該当するものを除く)。[A]重合体は、構造単位(IV)を有することで、露光後における現像液への溶解性が向上する。その結果、当該感放射線性樹脂組成物のMEEF性能及びブリッジ等欠陥抑制性が向上する。
上記式(m-4-1)中、R41は、式(4-1)と同義である。
構造単位(V)は、アルカリ反応性基を有する構造単位である(但し、構造単位(II-3)に該当するものを除く)。[A]重合体が構造単位(V)を有することで、当該感放射線性樹脂組成物から形成されるレジスト被膜の現像液に対する溶解性を高めることができる。構造単位(V)における上記アルカリ反応性基としては、ラクトン構造又は環状カーボネート構造を有する基が好ましい。
構造単位(V-1)は、上記構造単位(V)のアルカリ反応性基がラクトン構造を有する基である構造単位である。構造単位(V-1)の例としては、例えば、下記式(5a-1)~(5a-6)で表される構造単位を挙げることができる。
構造単位(V-2)は、上記構造単位(V)のアルカリ反応性基が、環状カーボネート構造を有する基である構造単位である。構造単位(V-2)の例としては、例えば、下記式(5b)で表される構造単位を挙げることができる。
ここで、本発明における[A]重合体を構成する全構造単位に対する上記各構造単位の好ましい含有割合を以下に示す。
構造単位(I)の含有割合は、当該感放射線性樹脂組成物のMEEF性能及びブリッジ等の欠陥抑制性がさらに向上する観点から、10~90モル%であることが好ましく、より好ましくは20~80モル%、さらに好ましくは30~80モル%である。
上記構造単位(II)の含有割合は、レジスト被膜からの酸発生剤等の液浸露光液に対する溶出抑制性、及びレジスト被膜と液浸露光液との後退接触角をさらに効率的に高める観点から、20~90モル%であることが好ましく、より好ましくは20~80モル%、さらに好ましくは20~70モル%である。
上記構造単位(IV)の含有割合は、当該感放射線性樹脂組成物のMEEF性能及びブリッジ等の欠陥抑制性がさらに向上する観点から、通常50モル%以下、好ましくは5~30モル%、さらに好ましくは5~20モル%である。
上記構造単位(V)の含有割合は、当該感放射線性樹脂組成物から形成されるレジスト被膜の現像液に対する親和性向上の観点から、通常50モル%以下、好ましくは5~30モル%、さらに好ましくは5~20モル%である。
[A]重合体におけるフッ素原子含有量は、[A]重合体全体を100質量%として、5質量%以上であり、好ましくは5~50質量%、さらに好ましくは5~40質量%である。なお、このフッ素原子含有量は13C-NMRにより測定することができる。[A]重合体におけるフッ素原子含有量が上記範囲内であると、[A]重合体及び後述する[B]重合体を含有する感放射線性樹脂組成物によって形成されたレジスト塗膜表面の撥水性を高めることができ、液浸露光時に上層膜を別途形成する必要がなくなる。
[A]重合体は、例えば、所定の各構造単位を与える重合性不飽和単量体を、ヒドロパーオキシド類、ジアルキルパーオキシド類、ジアシルパーオキシド類、アゾ化合物等のラジカル重合開始剤を使用し、必要に応じて連鎖移動剤の存在下、適当な溶媒中で重合することにより合成することができる。
液々抽出に用いる溶剤としては、例えば、n-ペンタン、n-ヘキサン、n-ヘプタン、n-オクタン、n-ノナン、n-デカン等のアルカン類;メタノール、エタノール、1-プロパノール、2-プロパノール、4-メチル-2-ペンタノール等のアルコール類;アセトン、2-ブタノン、4-メチル-2-ペンタノン、2-ヘプタノン等のケトン類等を挙げることができる。これらのなかでも、n-ヘキサン、n-ヘプタン、メタノール、エタノール、アセトン、及び2-ブタノンが好ましい。
[B]重合体は、酸解離性基を有し、フッ素原子含有量が5質量%未満である重合体である。[B]重合体は、この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。[B]重合体の酸解離性基としては特に限定されないが、その構造中に環状炭化水素基を有する基であることが好ましい。環状炭化水素基を有する酸解離性基を含む[B]重合体は、酸解離性基が容易に解離するため、感度が高くなるという利点がある。
[B]重合体におけるフッ素原子含有量は、5質量%未満であり、好ましくは0~4.9質量%、さらに好ましくは0~4質量%である。なお、このフッ素原子含有量は13C-NMRにより測定することができる。[B]重合体におけるフッ素原子含有量が上記範囲内とすることで、[B]重合体及び上述の[A]重合体を含む感放射線性樹脂組成物によって形成されたレジスト塗膜表面の撥水性を高めることができ、液浸露光時に上層膜を別途形成する必要がなくなる。
[B]重合体は、例えば、所定の各構造単位を与える重合性不飽和単量体を、ヒドロパーオキシド類、ジアルキルパーオキシド類、ジアシルパーオキシド類、アゾ化合物等のラジカル重合開始剤を使用し、必要に応じて連鎖移動剤の存在下、適当な溶媒中で重合することにより合成することができる。
これらの溶媒は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
本発明の感放射線性樹脂組成物には、[A]重合体、[B]重合体及び[C]酸発生剤以外にも、必要に応じて、酸拡散制御剤、溶媒、各種の添加剤(例えば、脂環族添加剤、界面活性剤、ラクトン化合物等)等の任意成分を含有させることができる。
酸拡散制御剤としては、例えば、下記式(6)で表される化合物(以下、「含窒素化合物(I)」ともいう。)、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)」ともいう。)、窒素原子を3個以上有する化合物(以下、「含窒素化合物(III)」ともいう。)、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。当該感放射線性樹脂組成物は、酸拡散制御剤を含有することにより、レジストとしてのパターン形状の良好性や寸法忠実度を向上させることができる。
脂環族添加剤は、ドライエッチング耐性、パターン形状、基板との接着性等をさらに改善する作用を示す成分である。このような脂環族添加剤としては、例えば、1-アダマンタンカルボン酸t-ブチル、1-アダマンタンカルボン酸t-ブトキシカルボニルメチル、1,3-アダマンタンジカルボン酸ジ-t-ブチル、1-アダマンチル酢酸t-ブチル、1-アダマンチル酢酸t-ブトキシカルボニルメチル、1,3-アダマンチレンジ酢酸ジ-t-ブチル等のアダマンタン誘導体類;デオキシコール酸t-ブチル、デオキシコール酸t-ブトキシカルボニルメチル、デオキシコール酸2-エトキシエチル、デオキシコール酸2-シクロヘキシルオキシエチル、デオキシコール酸3-オキソシクロヘキシル、デオキシコール酸テトラヒドロピラニル、デオキシコール酸メバロノラクトンエステル等のデオキシコール酸エステル類;リトコール酸t-ブチル、リトコール酸t-ブトキシカルボニルメチル、リトコール酸2-エトキシエチル、リトコール酸2-シクロヘキシルオキシエチル、リトコール酸3-オキソシクロヘキシル、リトコール酸テトラヒドロピラニル、リトコール酸メバロノラクトンエステル等のリトコール酸エステル類等を挙げることができる。これらの脂環族添加剤は、1種単独で又は2種以上を混合して使用することができる。脂環族添加剤の含有量は、[B]重合体100質量部に対して、通常、50質量部以下であり、好ましくは30質量部以下である。
界面活性剤は、塗布性、現像性等を改良する作用を示す成分である。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-オクチルフェニルエーテル、ポリオキシエチレンn-ノニルフェニルエーテル、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のノニオン系界面活性剤のほか、以下商品名で、KP341(信越化学工業社製)、ポリフローNo.75、同No.95(以上、共栄社化学社製)、エフトップEF301、同EF303、同EF352(以上、トーケムプロダクツ社製)、メガファックF171、同F173(以上、大日本インキ化学工業社製)、フロラードFC430、同FC431(以上、住友スリーエム社製)、アサヒガードAG710、サーフロンS-382、同SC-101、同SC-102、同SC-103、同SC-104、同SC-105、同SC-106(以上、旭硝子社製)等を挙げることができる。これらの界面活性剤は、1種単独で又は2種以上を混合して使用することができる。界面活性剤の含有量は、[B]重合体100質量部に対して、通常、2質量部以下である。
ラクトン化合物は、[A]重合体を、効率的にレジスト膜表面に偏析させる効果を有するものである。そのため、このラクトン化合物を含有させることで、[A]重合体の添加量を従来よりも少なくすることができる。従って、LWR(Line Width Roughness)良好性、現像欠陥抑制性、パターン倒れ耐性等のレジスト基本特性を損なうことなく、レジスト膜から液浸液への成分の溶出を抑制したり、液浸露光における高速スキャンにおいても液滴の残留が抑制され、結果として、レジスト膜表面の撥水性を維持しつつ、ウォーターマーク欠陥等の液浸露光に起因する欠陥を抑制することができる。
当該感放射線性樹脂組成物は、例えば、[A]重合体、[B]重合体及び[C]酸発生剤、及び必要に応じて任意成分を所定の割合で混合することにより調製できる。当該感放射線性樹脂組成物は、通常、その使用に際して、全固形分濃度が1~50質量%、好ましくは3~25質量%となるように溶媒に溶解した後、例えば孔径0.02μm程度のフィルターでろ過することによって、組成物溶液として調製される。
本発明のレジストパターンの形成方法は、(1)当該感放射線性樹脂組成物を用いて基板上にフォトレジスト膜を形成する工程(以下、「工程(1)」ともいう。)、(2)上記フォトレジスト膜上に液浸露光用液体を配置し、この液浸露光用液体を介して上記フォトレジスト膜を液浸露光する工程(以下、「工程(2)」ともいう。)、及び(3)液浸露光された上記フォトレジスト膜を現像してレジストパターンを形成する工程(以下、「工程(3)」ともいう。)を有する。当該レジストパターンの形成方法によれば、良好なパターン形状のレジストパターンを形成することができる。
上記有機溶媒としては、例えば、アセトン、2-ブタノン、メチルi-ブチルケトン、シクロペンタノン、シクロヘキサノン、3-メチルシクロペンタノン、2,6-ジメチルシクロヘキサノン等のケトン類;メチルアルコール、エチルアルコール、n-プロピルアルコール、i-プロピルアルコール、n-ブチルアルコール、t-ブチルアルコール、シクロペンタノール、シクロヘキサノール、1,4-ヘキサンジオール、1,4-ヘキサンジメチロール等のアルコール類;テトラヒドロフラン、ジオキサン等のエーテル類;酢酸エチル、酢酸n-ブチル、酢酸i-アミル等のエステル類;トルエン、キシレン等の芳香族炭化水素類の他、フェノール、アセトニルアセトン、ジメチルホルムアミド等を挙げることができる。これらの有機溶媒は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
本発明の重合体は、上記式(1-1)及び(1-2)でそれぞれ表される複数の構造単位からなる群より選択される少なくとも1種の構造単位(I)を有し、フッ素原子含有量が5質量%以上である重合体である。
上記式(1-1)中、Yは、(2+d)価の飽和炭化水素基である。R2及びR3は、それぞれ独立して、アルキル基である。但し、R2及びR3が互いに結合してYと共に脂環式構造を形成していてもよい。R4は、アルキル基、アルコキシ基、アシル基又はアシロキシ基である。R3又はR4が複数存在する場合、複数のR3及びR4はそれぞれ同一でも異なっていてもよい。R4の水素原子の一部又は全部が置換されていてもよい。aは、1又は2である。bは、0~3の整数である。dは、1又は2である。
上記式(1-2)中、R5は、アルキル基である。R6は、アルキル基、アルコキシ基、アシル基又はアシロキシ基である。R6が複数存在する場合、複数のR6は同一でも異なっていてもよい。R6の水素原子の一部又は全部が置換されていてもよい。eは1又は2である。fは0~5の整数である。
[A]重合体及び[B]重合体のMw及びMnは、東ソー社製のGPCカラム(G2000HXL2本、G3000HXL1本、G4000HXL1本)を用い、流量1.0mL/分、溶出溶媒としてテトラヒドロフランを用い、カラム温度40℃の分析条件で、単分散ポリスチレンを標準とするゲルパーミエーションクロマトグラフィ(GPC)により測定した。また、Mw及びMnの測定結果から分散度(Mw/Mn)を算出した。
[A]重合体及び[B]重合体の13C-NMR分析は、日本電子社製「JNM-EX270」を用いて行った。
[A]重合体(重合体(A-1)~(A-11))の合成に用いた単量体(化合物(M-1)~(M-9))を以下に示す。
なお、下記化合物(M-1)~(M-4)は、上述の構造単位(1-1)及び(1-2)を与える単量体であり、下記化合物(M-6)及び(M-9)は、上述の構造単位(2-1)~(2-3)を与える単量体である。
(重合体(A-1)の合成)
まず、単量体として上記化合物(M-1)60モル%、化合物(M-7)25モル%、化合物(M-8)15モル%、及び、開始剤(2,2’-アゾビスイソブチロニトリル(AIBN))を50gの2-ブタノンに溶解した単量体溶液を準備した。仕込みの単量体の合計量は50gとした。なお、各単量体のモル%は単量体全量に対するモル%を表し、開始剤の使用割合は、単量体と開始剤の合計量に対して、5モル%とした。
一方、温度計及び滴下漏斗を備えた500mLの三つ口フラスコに2-ブタノン50gを加え、30分間窒素パージを行った。その後、フラスコ内をマグネティックスターラーで攪拌しながら、80℃になるように加熱した。
次いで、上記単量体溶液をフラスコ内に、滴下漏斗を用いて3時間かけて滴下した。滴下後3時間熟成させ、その後、30℃以下になるまで冷却して重合体溶液を得た。
それから、重合体溶液を2L分液漏斗に移液した後、150gのn-ヘキサンでその重合体溶液を均一に希釈し、600gのメタノールを投入して混合した。次いで、30gの蒸留水を投入した後、攪拌して30分静置した。その後、下層を回収し、プロピレングリコールモノメチルエーテルアセテート溶液とした。このプロピレングリコールモノメチルエーテルアセテート溶液中の重合体を重合体(A-1)とする。
この重合体(A-1)は、Mwが6,000であり、Mw/Mnが1.7であった。13C-NMR分析の結果、重合体(A-1)は、各単量体に由来する各構造単位の含有比率[(M-1):(M-7):(M-8)]が、58.8:23.4:17.8(モル%)の共重合体であった。
(重合体(A-2)~(A-11)の合成)
合成例1において、下記表1に示す種類及び配合比の単量体化合物を用いたこと以外は、合成例1と同様にして、重合体(A-2)~(A-11)を合成した。得られた各重合体について、各単量体に由来する構造単位の含有比率、重量平均分子量(Mw)及び分散度(Mw/Mn)を測定した。これらの測定値を表2に示す。
[B]重合体(重合体(B-1)及び(B-2))の合成に用いた単量体(化合物(M-A)~(M-F))を以下に示す。
(重合体(B-1)の合成)
上記化合物(M-A)31.63g(35モル%)、上記化合物(M-B)12.32g(10モル%)、上記化合物(M-C)6.45g(10モル%)、及び上記化合物(M-D)49.60g(45モル%)を、2-ブタノン200gに溶解し、さらに2,2’-アゾビスイソブチロニトリル8.14g(単量体の全体量に対して10モル%)を加えて単量体溶液を得た。
一方、100gの2-ブタノンを仕込んだ500mLの三口フラスコを30分窒素パージした。窒素パージの後、フラスコ内を攪拌しながら80℃に加熱し、上記単量体溶液を滴下漏斗を用いて3時間かけて滴下した。滴下開始を重合開始時間とし、重合反応を6時間行った。重合終了後、重合体溶液は、水冷によって30℃以下に冷却し、4,000gのメタノールに投入して白色粉末を析出させた。その後、析出した白色粉末をろ別した。ろ別された白色粉末を800gのメタノールを用いてスラリー状にすることで2回洗浄した後、ろ別した。その後、50℃で17時間乾燥し、白色粉末の重合体(B-1)を得た(70g、収率70%)。
この重合体(B-1)は、Mwが4,300であり、Mw/Mnが1.3であった。13C-NMR分析の結果、重合体(B-1)は、各単量体に由来する各構造単位の含有比率[(M-A):(M-B):(M-C):(M-D)]が、36.8:9.4:10.2:43.6(モル%)の共重合体であった。
(重合体(B-2)の合成)
合成例12において、下記表3に示す種類及び配合比の化合物(単量体)を用いたこと、及びAIBNをモノマー量に対して5モル%使用したこと以外は、合成例12と同様にして、重合体(B-2)を合成した。
当該感放射線性樹脂組成物を構成する上記合成した[A]重合体及び[B]重合体以外の成分([C]酸発生剤、[D]酸拡散制御剤、[E]溶媒)について、以下に示す。
(C-1):4-シクロヘキシルフェニルジ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(下記式(C-1)で表される化合物)
(C-2):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(下記式(C-2)で表される化合物)
(D-1):N-t-ブトキシカルボニル-4-ヒドロキシピペリジン
(D-2):2-フェニルベンゾイミダゾール
(E-1):プロピレングリコールモノメチルエーテルアセテート
(E-2):シクロヘキサノン
(F-1):γ-ブチロラクトン
重合体(A-1)3部、重合体(B-1)100部、酸発生剤(C-1)12部、酸拡散制御剤(D-1)1部、溶媒(E-1)1,360部及び溶媒(E-2)580部、並びにラクトン化合物(F-1)30部を混合して、実施例1の感放射線性樹脂組成物を調製した。
実施例1において、各成分を下記表5に示す種類及び配合量で混合した以外は、実施例1と同様にして、実施例2~10及び比較例1~3の感放射線性樹脂組成物を調製した。
実施例1~10及び比較例1~3の各感放射線性樹脂組成物について、下記(1)及び(2)の評価方法に従い、ブリッジ欠陥及びマスクエラーファクター(MEEF)性能についての評価を行った。これらの評価結果を表6に示す。
基板として、表面に膜厚77nmの下層反射防止膜(「ARC29A」、ブルワー・サイエンス社製)を形成した12インチシリコンウェハを用いた。なお、この反射防止膜の形成には、スピンコーター(「CLEAN TRACK ACT12」、東京エレクトロン社製)を用いた。
次いで、上記実施例及び比較例で得られた感放射線性樹脂組成物を上記基板上に、上記CLEAN TRACK ACT12にて、スピンコートし、120℃で60秒間プレベーク(PB)を行うことにより、膜厚150nmのレジスト被膜を形成した。このレジスト被膜に、ArFエキシマレーザー液浸露光装置(「ASML AT1250i」、ASML製)をNA=0.85、σ0/σ1=0.96/0.76、Annularにより、マスクパターンを介して露光した。この際、レジスト上面と液浸露光機レンズとの間の液浸溶媒としては純水を用いた。その後、95℃で60秒間ポストエクスポージャーベーク(PEB)を行ったのち、2.38質量%のテトラメチルアンモニウムヒドロキシド水溶液により、23℃で60秒間現像し、水洗し、乾燥して、ポジ型のレジストパターンを形成した。このとき、線幅100nmのライン・アンド・スペースパターン(1L1S)を1対1の線幅に形成する露光量を最適露光量とし、この最適露光量を感度とした。なお、この測長には走査型電子顕微鏡(「S-9380」、日立ハイテクノロジーズ社製)を用いた。
その後、線幅100nmのライン・アンド・スペースパターン(1L1S)上の欠陥数を、欠陥検査装置(KLA-Tencor社製「KLA2351」)を用いて測定した。さらに、「KLA2351」にて測定された欠陥を、走査型電子顕微鏡(「S-9380」、日立ハイテクノロジーズ社製)を用いて観察し、ブリッジタイプの欠陥を区別し、それらの欠陥数の合計が100個/wafer以上であった場合を「不良」とし、100個/wafer未満であった場合は「良好」として評価した。評価結果を表6に示す。
まず、下層反射防止膜(「ARC66」、日産化学社製)を形成した12インチシリコンウェハ上に、上記実施例及び比較例で得られた感放射線性樹脂組成物によって、膜厚110nmの被膜を形成し、120℃で60秒間PBを行った。次に、この被膜を、ArFエキシマレーザー液浸露光装置(「NSR S610C」、NIKON社製)を用い、NA=1.3、ratio=0.800、Dipoleの条件により、マスクパターンを介して露光した。
Claims (8)
- [A]下記式(1-1)及び(1-2)でそれぞれ表される複数の構造単位からなる群より選択される少なくとも1種の構造単位(I)を有し、フッ素原子含有量が5質量%以上である重合体、
[B]酸解離性基を有し、フッ素原子含有量が5質量%未満である重合体、及び
[C]感放射線性酸発生剤
を含有する感放射線性樹脂組成物。
式(1-1)中、Yは、(2+d)価の飽和炭化水素基である。R2及びR3は、それぞれ独立して、アルキル基である。但し、R2及びR3が互いに結合してYと共に脂環式構造を形成していてもよい。R4は、アルキル基、アルコキシ基、アシル基又はアシロキシ基である。R3又はR4が複数存在する場合、複数のR3及びR4はそれぞれ同一でも異なっていてもよい。R4の水素原子の一部又は全部が置換されていてもよい。aは、1又は2である。bは、0~3の整数である。dは、1又は2である。
式(1-2)中、R5は、アルキル基である。R6は、アルキル基、アルコキシ基、アシル基又はアシロキシ基である。R6が複数存在する場合、複数のR6は同一でも異なっていてもよい。R6の水素原子の一部又は全部が置換されていてもよい。eは1又は2である。fは0~5の整数である。) - [A]重合体が、下記式(2-1)~(2-3)でそれぞれ表される複数の構造単位からなる群より選択される少なくとも1種の構造単位(II)をさらに有する請求項1に記載の感放射線性樹脂組成物。
式(2-1)中、Rf1は、炭素数1~30のフッ素化炭化水素基である。
式(2-2)中、R7は、(g+1)価の連結基である。R8は、水素原子又は1価の有機基である。R8が複数存在する場合、複数のR8は同一でも異なっていてもよい。Rf2及びRf3は、それぞれ独立して、水素原子、フッ素原子又は炭素数1~30のフッ素化炭化水素基である。但し、Rf2及びRf3の両方が共に水素原子である場合である場合はない。Rf2又はRf3が複数存在する場合、複数のRf2及びRf3はそれぞれ同一でも異なっていてもよい。gは、1~3の整数である。
式(2-3)中、R9は2価の連結基である。R10は、水素原子又は1価の有機基である。Rf4及びRf5は、それぞれ独立して、水素原子、フッ素原子又は炭素数1~30のフッ素化炭化水素基である。但し、Rf4及びRf5の両方が共に水素原子である場合である場合はない。) - [B]重合体100質量部に対する[A]重合体の含有量が、0.1質量部以上20質量部以下である請求項1に記載の感放射線性樹脂組成物。
- 下記式(1-1)及び(1-2)でそれぞれ表される複数の構造単位からなる群より選択される少なくとも1種の構造単位(I)を有し、フッ素原子含有量が5質量%以上である重合体。
式(1-1)中、Yは、(2+d)価の飽和炭化水素基である。R2及びR3は、それぞれ独立して、アルキル基である。但し、R2及びR3が互いに結合してYと共に脂環式構造を形成していてもよい。R4は、アルキル基、アルコキシ基、アシル基又はアシロキシ基である。R3又はR4が複数存在する場合、複数のR3及びR4はそれぞれ同一でも異なっていてもよい。R4の水素原子の一部又は全部が置換されていてもよい。aは、1又は2である。bは、0~3の整数である。dは、1又は2である。
式(1-2)中、R5は、アルキル基である。R6は、アルキル基、アルコキシ基、アシル基又はアシロキシ基である。R6が複数存在する場合、複数のR6は同一でも異なっていてもよい。R6の水素原子の一部又は全部が置換されていてもよい。eは1又は2である。fは0~5の整数である。) - 下記式(2-1)~(2-3)でそれぞれ表される複数の構造単位からなる群より選択される少なくとも1種の構造単位(II)をさらに有する請求項5に記載の重合体。
式(2-1)中、Rf1は、炭素数1~30のフッ素化炭化水素基である。
式(2-2)中、R7は、(g+1)価の連結基である。R8は、水素原子又は1価の有機基である。R8が複数存在する場合、複数のR8は同一でも異なっていてもよい。Rf2及びRf3は、それぞれ独立して、水素原子、フッ素原子又は炭素数1~30のフッ素化炭化水素基である。但し、Rf2及びRf3の両方が共に水素原子である場合である場合はない。Rf2又はRf3が複数存在する場合、複数のRf2及びRf3はそれぞれ同一でも異なっていてもよい。gは、1~3の整数である。
式(2-3)中、R9は2価の連結基である。R10は、水素原子又は1価の有機基である。Rf4及びRf5は、それぞれ独立して、水素原子、フッ素原子又は炭素数1~30のフッ素化炭化水素基である。但し、Rf4及びRf5の両方が共に水素原子である場合である場合はない。) - (1)請求項1から請求項4のいずれか1項に記載の感放射線性樹脂組成物を用いて基板上にフォトレジスト膜を形成する工程、
(2)上記フォトレジスト膜上に液浸露光用液体を配置し、この液浸露光用液体を介して上記フォトレジスト膜を液浸露光する工程、及び
(3)液浸露光された上記フォトレジスト膜を現像してレジストパターンを形成する工程
を有するレジストパターン形成方法。
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Publication number | Priority date | Publication date | Assignee | Title |
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US20120100483A1 (en) * | 2010-10-26 | 2012-04-26 | Sumitomo Chemical Company, Limited | Resist composition and method for producing resist pattern |
WO2015037520A1 (ja) * | 2013-09-12 | 2015-03-19 | Jsr株式会社 | 樹脂組成物、レジストパターン形成方法及び重合体 |
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WO2011062168A1 (ja) * | 2009-11-18 | 2011-05-26 | Jsr株式会社 | 感放射線性樹脂組成物、重合体及びレジストパターン形成方法 |
JP5910445B2 (ja) * | 2012-09-28 | 2016-04-27 | Jsr株式会社 | 液浸上層膜形成用組成物及びレジストパターン形成方法 |
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KR20200031257A (ko) * | 2018-09-14 | 2020-03-24 | 도오꾜오까고오교 가부시끼가이샤 | 레지스트 조성물 및 레지스트 패턴 형성 방법 |
EP3919981A4 (en) * | 2019-01-28 | 2022-03-30 | FUJIFILM Corporation | ACTINIC LIGHT OR RADIATION SENSITIVE RESIN COMPOSITION, RESIST FILM, PATTERN FORMING METHOD, AND ELECTRONIC DEVICE PRODUCTION METHOD |
TWI791224B (zh) * | 2021-05-26 | 2023-02-01 | 達興材料股份有限公司 | 鹼可溶性樹脂、保護層組成物、保護層、積層體以及光阻圖案的形成方法 |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5993448A (ja) | 1982-09-30 | 1984-05-29 | ブリューワー・サイエンス・インコーポレイテッド | 反射防止コ−テイング |
JPH05188598A (ja) | 1991-06-28 | 1993-07-30 | Internatl Business Mach Corp <Ibm> | 表面反射防止コーティングフィルム |
JPH0612452A (ja) | 1992-06-25 | 1994-01-21 | Hitachi Ltd | グループ情報アクセス方式 |
JP2005173474A (ja) | 2003-12-15 | 2005-06-30 | Tokyo Ohka Kogyo Co Ltd | 液浸露光プロセス用レジスト組成物、該レジスト材料を用いたレジストパターン形成方法 |
JP2005352384A (ja) | 2004-06-14 | 2005-12-22 | Fuji Photo Film Co Ltd | 液浸露光用保護膜形成組成物及びそれを用いたパターン形成方法 |
JP2006048029A (ja) | 2004-07-07 | 2006-02-16 | Fuji Photo Film Co Ltd | 液浸露光用ポジ型レジスト組成物及びそれを用いたパターン形成方法 |
US20060216643A1 (en) * | 2004-01-08 | 2006-09-28 | International Business Machines Corporation | Positive photoresist composition with a polymer including a fluorosulfonamide group and process for its use |
WO2007116664A1 (ja) | 2006-03-31 | 2007-10-18 | Jsr Corporation | フッ素含有重合体及び精製方法並びに感放射線性樹脂組成物 |
JP2008308546A (ja) | 2007-06-13 | 2008-12-25 | Tokyo Ohka Kogyo Co Ltd | 高分子化合物、ポジ型レジスト組成物およびレジストパターン形成方法 |
JP2008308545A (ja) | 2007-06-13 | 2008-12-25 | Tokyo Ohka Kogyo Co Ltd | 高分子化合物、ポジ型レジスト組成物およびレジストパターン形成方法 |
JP2009134088A (ja) | 2007-11-30 | 2009-06-18 | Jsr Corp | 感放射線性樹脂組成物 |
EP2088466A1 (en) * | 2008-02-06 | 2009-08-12 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition for immersion exposure, method of forming resist pattern using the same, and fluorine-containing compound |
JP2009191151A (ja) * | 2008-02-14 | 2009-08-27 | Shin Etsu Chem Co Ltd | 高分子化合物、レジスト材料、及びパターン形成方法 |
JP2010139662A (ja) * | 2008-12-10 | 2010-06-24 | Tokyo Ohka Kogyo Co Ltd | レジスト組成物、レジストパターン形成方法、新規な化合物および酸発生剤 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4822718A (en) | 1982-09-30 | 1989-04-18 | Brewer Science, Inc. | Light absorbing coating |
US4910122A (en) | 1982-09-30 | 1990-03-20 | Brewer Science, Inc. | Anti-reflective coating |
US5674648A (en) | 1984-08-06 | 1997-10-07 | Brewer Science, Inc. | Anti-reflective coating |
US6280897B1 (en) * | 1996-12-24 | 2001-08-28 | Kabushiki Kaisha Toshiba | Photosensitive composition, method for forming pattern using the same, and method for manufacturing electronic parts |
JP4716016B2 (ja) * | 2005-12-27 | 2011-07-06 | 信越化学工業株式会社 | 高分子化合物、レジスト材料、及びパターン形成方法 |
US7476492B2 (en) | 2006-05-26 | 2009-01-13 | International Business Machines Corporation | Low activation energy photoresist composition and process for its use |
EP1975705B1 (en) * | 2007-03-28 | 2016-04-27 | FUJIFILM Corporation | Positive resist composition and pattern-forming method |
KR100991312B1 (ko) * | 2007-08-30 | 2010-11-01 | 샌트랄 글래스 컴퍼니 리미티드 | 포지티브형 레지스트 조성물 |
JP5555914B2 (ja) * | 2007-10-29 | 2014-07-23 | Jsr株式会社 | 感放射線性樹脂組成物 |
CN101526737B (zh) * | 2007-11-05 | 2014-02-26 | 罗门哈斯电子材料有限公司 | 浸渍平版印刷用组合物和浸渍平版印刷方法 |
WO2010029982A1 (ja) * | 2008-09-12 | 2010-03-18 | Jsr株式会社 | 感放射線性樹脂組成物及びレジストパターン形成方法 |
JP5346627B2 (ja) * | 2009-03-10 | 2013-11-20 | 東京応化工業株式会社 | ポジ型レジスト組成物及びレジストパターン形成方法 |
KR20100121427A (ko) * | 2009-05-07 | 2010-11-17 | 제이에스알 가부시끼가이샤 | 감방사선성 수지 조성물 |
JP5386236B2 (ja) | 2009-06-01 | 2014-01-15 | 東京応化工業株式会社 | ポジ型レジスト組成物及びレジストパターン形成方法 |
JP2010275498A (ja) * | 2009-06-01 | 2010-12-09 | Central Glass Co Ltd | 含フッ素化合物、含フッ素高分子化合物、レジスト組成物、トップコート組成物及びパターン形成方法 |
WO2011062168A1 (ja) * | 2009-11-18 | 2011-05-26 | Jsr株式会社 | 感放射線性樹脂組成物、重合体及びレジストパターン形成方法 |
JP5540757B2 (ja) * | 2010-02-18 | 2014-07-02 | Jsr株式会社 | 重合体の製造方法 |
-
2010
- 2010-11-16 WO PCT/JP2010/070412 patent/WO2011062168A1/ja active Application Filing
- 2010-11-16 CN CN201410593866.8A patent/CN104391429B/zh active Active
- 2010-11-16 EP EP10831562.3A patent/EP2503392B1/en active Active
- 2010-11-16 CN CN201080045526.1A patent/CN102597878B/zh active Active
- 2010-11-16 KR KR1020127009977A patent/KR101412329B1/ko active IP Right Grant
- 2010-11-16 JP JP2011541929A patent/JP5758301B2/ja active Active
- 2010-11-17 TW TW099139516A patent/TWI476212B/zh active
-
2012
- 2012-05-17 US US13/473,957 patent/US9598520B2/en active Active
-
2015
- 2015-04-30 JP JP2015093488A patent/JP6048532B2/ja active Active
- 2015-04-30 JP JP2015093489A patent/JP5954459B2/ja active Active
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5993448A (ja) | 1982-09-30 | 1984-05-29 | ブリューワー・サイエンス・インコーポレイテッド | 反射防止コ−テイング |
JPH05188598A (ja) | 1991-06-28 | 1993-07-30 | Internatl Business Mach Corp <Ibm> | 表面反射防止コーティングフィルム |
JPH0612452A (ja) | 1992-06-25 | 1994-01-21 | Hitachi Ltd | グループ情報アクセス方式 |
JP2005173474A (ja) | 2003-12-15 | 2005-06-30 | Tokyo Ohka Kogyo Co Ltd | 液浸露光プロセス用レジスト組成物、該レジスト材料を用いたレジストパターン形成方法 |
US20060216643A1 (en) * | 2004-01-08 | 2006-09-28 | International Business Machines Corporation | Positive photoresist composition with a polymer including a fluorosulfonamide group and process for its use |
JP2005352384A (ja) | 2004-06-14 | 2005-12-22 | Fuji Photo Film Co Ltd | 液浸露光用保護膜形成組成物及びそれを用いたパターン形成方法 |
JP2006048029A (ja) | 2004-07-07 | 2006-02-16 | Fuji Photo Film Co Ltd | 液浸露光用ポジ型レジスト組成物及びそれを用いたパターン形成方法 |
WO2007116664A1 (ja) | 2006-03-31 | 2007-10-18 | Jsr Corporation | フッ素含有重合体及び精製方法並びに感放射線性樹脂組成物 |
JP2008308546A (ja) | 2007-06-13 | 2008-12-25 | Tokyo Ohka Kogyo Co Ltd | 高分子化合物、ポジ型レジスト組成物およびレジストパターン形成方法 |
JP2008308545A (ja) | 2007-06-13 | 2008-12-25 | Tokyo Ohka Kogyo Co Ltd | 高分子化合物、ポジ型レジスト組成物およびレジストパターン形成方法 |
JP2009134088A (ja) | 2007-11-30 | 2009-06-18 | Jsr Corp | 感放射線性樹脂組成物 |
EP2088466A1 (en) * | 2008-02-06 | 2009-08-12 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition for immersion exposure, method of forming resist pattern using the same, and fluorine-containing compound |
JP2009191151A (ja) * | 2008-02-14 | 2009-08-27 | Shin Etsu Chem Co Ltd | 高分子化合物、レジスト材料、及びパターン形成方法 |
JP2010139662A (ja) * | 2008-12-10 | 2010-06-24 | Tokyo Ohka Kogyo Co Ltd | レジスト組成物、レジストパターン形成方法、新規な化合物および酸発生剤 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2503392A4 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120100483A1 (en) * | 2010-10-26 | 2012-04-26 | Sumitomo Chemical Company, Limited | Resist composition and method for producing resist pattern |
US9291893B2 (en) * | 2010-10-26 | 2016-03-22 | Sumitomo Chemical Company, Limited | Resist composition and method for producing resist pattern |
WO2015037520A1 (ja) * | 2013-09-12 | 2015-03-19 | Jsr株式会社 | 樹脂組成物、レジストパターン形成方法及び重合体 |
JPWO2015037520A1 (ja) * | 2013-09-12 | 2017-03-02 | Jsr株式会社 | 樹脂組成物、レジストパターン形成方法及び重合体 |
US10331031B2 (en) | 2013-09-12 | 2019-06-25 | Jsr Corporation | Resin composition, resist pattern-forming method and polymer |
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