Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
• • 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
• • 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
• • 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
• • 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 photoresist composition, a resist pattern forming method, and a polymer.
• a resist film is formed on a substrate with a photoresist composition containing a polymer having an acid-dissociable group, and the resist film is excimered through a mask pattern.
• a fine resist pattern is formed by exposing short-wavelength radiation such as a laser and removing an exposed portion with an alkali developer.
• the immersion exposure method has an advantage that the depth of focus is hardly lowered even when the numerical aperture (NA) of the lens is increased, and high resolution can be obtained.
• NA numerical aperture
• the photoresist composition used in the immersion exposure method it is possible to prevent degradation of the coating film performance and contamination of the lens by suppressing the elution of the acid generator from the resist film to the immersion medium. It is required to prevent the watermark from remaining by improving the receding contact angle and to enable high-speed scanning exposure.
• Japanese Patent Application Laid-Open No. 2005-352384 proposes a technique for forming an upper layer film (protective film) on a resist film, but requires a separate film formation step, which is complicated. . Therefore, methods for increasing the hydrophobicity of the resist film surface have been studied.
• International Publication No. 2007/116664 proposes a photoresist composition containing a fluorine-containing polymer having high hydrophobicity.
• Japanese Patent Application Laid-Open No. 2010-032994 proposes a fluorine atom-containing polymer that is hydrophobic during immersion exposure but decreases in hydrophobicity during alkali development.
• the solubility of the fluorine atom-containing polymer in the developer is not satisfactory, and the LWR performance (Line) is a value representing the variation in the line width of the resist pattern. Width (Roughness) and the pattern shape obtained are not fully satisfactory.
• the present invention has been made based on the circumstances as described above, and its purpose is to improve the receding contact angle of the resist film surface at the time of exposure in the immersion exposure process and at the time of alkali development. Is to provide a photoresist composition that can greatly reduce the receding contact angle, thereby suppressing the occurrence of development defects, forming a resist pattern having a small LWR and a good pattern shape.
• [A] a polymer having an acid dissociable group hereinafter, also referred to as “[A] polymer”
• [B] an acid generator and [C] a polymer having a structural unit (I) represented by the following formula (1) and containing a fluorine atom
• [C] polymer Is a photoresist composition containing (In Formula (1), R 1 and R 2 are each independently a hydrogen atom, a methyl group or a trifluoromethyl group.
• E 1 and E 2 are each independently an oxygen atom, * 1 ⁇ CO—O— or * 1 —CO—NH—, * 1 represents a site bonded to a carbon atom of an adjacent polymer chain, A represents an acid-dissociable group or an alkali-dissociable group in the linking chain G is a single bond or a (n + 1) -valent linking group, n is an integer of 1 to 3. When n is 2 or more, a plurality of A, E 2 and R 2 may be the same or different.
• the photoresist composition can form a resist pattern having a small LWR and a good pattern shape.
• the reason why the photoresist composition exhibits the above-described effect by having the above-described configuration is not necessarily clear, but, for example, the [C] polymer has the specific structure, so that the structural unit (I) has a linked structure.
• the chain is acid or alkali cleaved to lower the molecular weight, and the solubility in the developer is improved. As a result, it is considered that development defects can be suppressed while improving the receding contact angle on the resist film surface, and a resist pattern having a small LWR and a good shape can be formed.
• the fluorine atom content of the polymer is preferably higher than the fluorine atom content of the [A] polymer.
• the [C] polymer can be unevenly distributed on the surface of the resist film more effectively, and the resist film surface can exhibit a higher receding contact angle.
• the content of the polymer is preferably 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the [A] polymer.
• the photoresist composition of the present invention Since the photoresist composition of the present invention has the above-mentioned properties, it is suitably used for immersion exposure.
• the photoresist composition improves the receding contact angle of the resist film surface during exposure, and greatly reduces the receding contact angle during alkali development, thereby reducing development defects in the formed resist film. Occurrence can be suppressed, and a resist pattern having a small LWR and a good pattern shape can be formed.
• the structural unit (I) is preferably represented by the following formula (1-1).
• R 1 , R 2 , G and n are as defined in the above formula (1).
• a 1 is a divalent acid dissociable group.
• n is 2 or more, A plurality of A 1 and R 2 may be the same or different.
• the linking chain is effectively cleaved by the acid generated from the [B] acid generator upon exposure, and the molecular weight of the [C] polymer is reduced. Can do. Thereby, the solubility with respect to the alkali developing solution of the [C] polymer in an exposure part can be improved more, and generation
• G in the above formula (1-1) preferably has an acid dissociable group in the linking chain.
• G also to have an acid-dissociable group, [C] the molecular weight of the polymer is lowered more, further improve the solubility in an alkali developing solution [C] polymer in the exposed area, exposed It is possible to further suppress development defects such as bridge defects in the portion.
• a 1 is preferably represented by the following formula (2-1), (2-2) or (2-3).
• R 3 and R 5 each independently represents an alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or 6 to 6 carbon atoms.
• R 4 is an alkanediyl group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or 2 having 6 to 22 carbon atoms.
• a valent aromatic hydrocarbon group, provided that any two of R 3 to R 5 may be bonded to each other to form a ring structure together with the carbon atom to which they are bonded.
• R 6 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a carbon number 6 to 22 monovalent aromatic hydrocarbon groups.
• R 7 is a single bond, an alkanediyl group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 22 carbon atoms.
• any two of R 6 to R 8 may be bonded to each other to form a ring structure together with the carbon atom to which R 6 and R 8 are bonded.
• R 9 represents an alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a monovalent aromatic hydrocarbon having 6 to 22 carbon atoms. It is a group.
• R 10 is a single bond, an alkanediyl group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 22 carbon atoms.
• R 11 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 22 carbon atoms.
• any two of R 9 to R 11 may be bonded to each other to form a ring structure together with the carbon atom to which R 10 and R 11 are bonded.
• ** represents a bonding site with the ester group in the formula (1-1).
• some or all of the hydrogen atoms of R 3 to R 11 may be substituted.
• Any two of R 3 to R 5 in the above formula (2-1) are preferably bonded to each other to form a ring structure together with the carbon atoms to which they are bonded.
• a 1 as an acid-dissociable group having such a ring structure, the acid dissociation property of A 1 can be further increased, development defects can be further suppressed, and a resist pattern with a smaller LWR can be formed.
• the structural unit (I) is preferably represented by the following formula (1-2).
• R 1 , R 2 , E 1 , E 2 and n are as defined in the above formula (1).
• R A is a group having an alkali-dissociable group in the linking chain.
• Two R 12 s are each independently a single bond, a divalent chain hydrocarbon group having 1 to 10 carbon atoms or a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms.
• R 14 is a group in which at least one group selected from the group consisting of —SO— and —SO 2 — and a hydrocarbon group having 1 to 20 carbon atoms are combined, and R 14 is 2 having 1 to 20 carbon atoms.
• one X 0 is a hydrocarbon group of valence are each independently a single bond or a part or all of the hydrogen atoms are substituted with fluorine atoms carbon If 1 is a divalent chain hydrocarbon group of 20 .n is 2 or more, plural R 12, X 0, R A , R 14, E 2 and R 2 may be each be the same or different .)
• the connecting chain is effectively cleaved by an alkali developer, and the molecular weight of the [C] polymer can be reduced.
• the solubility with respect to the alkali developing solution of a [C] polymer can be improved more, generation
• R A in the above formula (1-2) is preferably a group represented by the following formula (1-3).
• R 15 represents a divalent hydrocarbon group which may have a fluorine atom.
• Two Y 0 s are each independently —O—, * 2 —O. —CO—, * 2 —CO—O—, * 2 —SO 2 —O—, where * 2 represents a site bonded to X 0 .
• RA alkali dissociation property of RA is further increased, the solubility of [C] polymer in an alkaline developer can be further improved, and the occurrence of development defects can be further suppressed.
• a resist pattern having a smaller LWR and a good pattern shape can be formed.
• the polymer preferably further has a structural unit other than the structural unit (I) and containing an acid-dissociable group.
• the solubility of the [C] polymer in the exposed area in the alkaline developer is further improved, and the occurrence of development defects in the exposed area is further suppressed. Can do.
• the polymer preferably further has a structural unit other than the structural unit (I) and containing an alkali-dissociable group.
• the [C] polymer further has such a structural unit, the affinity of the [C] polymer for an alkaline developer can be improved, and development defects can be further suppressed.
• the resist pattern forming method of the present invention comprises: A step of forming a resist film on a substrate using the photoresist composition; A step of exposing the resist film; and a step of developing the exposed resist film.
• the photoresist composition of the present invention since the photoresist composition of the present invention is used, it is possible to form a resist pattern with less development defects and excellent pattern shape and LWR.
• the exposure in the exposure step is performed through an immersion exposure liquid disposed on the resist film.
• liquid immersion exposure can be satisfactorily performed with a high receding contact angle.
• the polymer of the present invention is a polymer having a structural unit (I) represented by the following formula (1) and containing a fluorine atom.
• R 1 and R 2 are each independently a hydrogen atom, a methyl group or a trifluoromethyl group.
• E 1 and E 2 are each independently an oxygen atom, * 1 ⁇ CO—O— or * 1 —CO—NH—, * 1 represents a site bonded to a carbon atom of an adjacent polymer chain,
• A represents an acid-dissociable group or an alkali-dissociable group in the linking chain
• G is a single bond or a (n + 1) -valent linking group, n is an integer of 1 to 3.
• n is 2 or more, a plurality of A, E 2 and R 2 may be the same or different.
• the polymer has a fluorine atom and the structural unit (I) represented by the above formula (1), it can be suitably used as a component of the photoresist composition of the present invention.
• the “linking chain” refers to a chain composed of a plurality of atoms that connect G and E 2 .
• the “acid-dissociable group” refers to a group that substitutes a hydrogen atom of a polar group such as a carboxy group or a hydroxy group, and dissociates in the presence of an acid.
• the alkali dissociable group is a group that replaces a hydrogen atom in a polar functional group such as a hydroxy group or a carboxy group, and is in the presence of an alkali (for example, 2.38% by mass of tetramethylammonium hydroxide at 23 ° C. A group that dissociates in an aqueous solution.
• the photoresist composition, resist pattern forming method and polymer of the present invention in the immersion exposure process, the receding contact angle of the resist film surface during exposure can be improved, and receding contact during alkali development. As a result, it is possible to greatly reduce the corners, thereby suppressing development defects and forming a resist pattern having a small LWR and a good pattern shape. Therefore, the photoresist composition, the resist pattern forming method, and the polymer can be suitably used in a lithography process that requires further miniaturization.
• the photoresist composition of the present invention contains [A] polymer, [B] acid generator and [C] polymer. Moreover, the said photoresist composition can contain a [D] acid diffusion control body and a [E] solvent as a suitable component. Furthermore, the said photoresist composition may contain another arbitrary component, unless the effect of this invention is impaired. Hereinafter, each component will be described in detail.
• the polymer is a polymer having an acid dissociable group. Moreover, [A] polymer turns into a base polymer in the said photoresist composition.
• the “base polymer” refers to a polymer that is a main component of a polymer that constitutes a resist film formed from a photoresist composition, and preferably 50% of the total polymer that constitutes the resist film. A polymer occupying at least mass%.
• the specific structure of the polymer is not particularly limited as long as it is a polymer having a structural unit containing an acid-dissociable group (hereinafter also referred to as “structural unit (II)”).
• the polymer also has a structural unit (III) containing at least one structure selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure, in the structural unit other than the structural unit (II). It is preferable. Furthermore, the [A] polymer may have other structural units other than the structural unit (II) and the structural unit (III). In addition, the [A] polymer may have 2 or more types of each structural unit. Hereinafter, each structural unit will be described in detail.
• the structural unit (II) is a structural unit containing an acid dissociable group.
• the acid-dissociable group in the structural unit (II) is dissociated by the action of the acid generated from the [B] acid generator in the exposed portion, whereby the alkali development of the [A] polymer is performed. Since the solubility in the liquid changes, a resist pattern can be formed.
• the “acid-dissociable group” in the structural unit (II) refers to a group that replaces a hydrogen atom of a polar group such as a carboxy group or a hydroxy group, and dissociates in the presence of an acid.
• the structural unit (II) is not particularly limited as long as it contains an acid dissociable group, and examples thereof include a structural unit represented by the following formula (3).
• R 16 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R 17 to R 19 are each independently an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 4 to 20 carbon atoms. However, R 17 and R 18 may be bonded to each other to form a divalent alicyclic hydrocarbon group together with the carbon atom to which they are bonded.
• Examples of the alkyl group having 1 to 6 carbon atoms represented by R 17 to R 19 include a methyl group, an ethyl group, and a propyl group.
• Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R 17 to R 19 include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, an adamantyl group, and the like.
• Examples of the divalent alicyclic hydrocarbon group that R 17 and R 18 may be bonded to each other include a cyclopentanediyl group, a norbornanediyl group, an adamantanediyl group, and the like.
• Examples of the structural unit (II) include structural units represented by the following formulas (3-1) to (3-12).
• R 16 has the same meaning as the above formula (3).
• the content ratio of the structural unit (II) in the polymer is preferably 20 mol% to 80 mol%, more preferably 30 mol% to 70 mol%, based on all structural units constituting the [A] polymer. preferable.
• the said photoresist composition can improve a sensitivity etc. more.
• the polymer preferably further has a structural unit (III) containing at least one structure selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure. [A] When the polymer further has the structural unit (III), adhesion of the resist film to the substrate can be improved.
• Examples of the structural unit (III) include structural units represented by the following formulas (4-1) to (4-14).
• R L1 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• the content ratio of the structural unit (III) in the polymer is preferably 10 mol% or more and 65 mol% or less, and 15 mol% or more and 60 mol% or less with respect to all the structural units constituting the [A] polymer. Is more preferable.
• the polymer may further have other structural units such as a structural unit containing a fluorine atom, a structural unit containing a polar group, and the like.
• a polar group a carboxy group, a hydroxy group and the like are preferable.
• content of the [A] polymer in the said photoresist composition it is 70 mass% or more normally with respect to the total solid (component except a solvent) in the said photoresist composition, and is 80 mass% or more. Is preferred.
• the polymer can be synthesized according to a conventional method such as radical polymerization using a monomer or the like that gives a structural unit containing an acid-dissociable group.
• Examples of the synthesis method include a method in which a solution containing a monomer and a radical initiator is dropped into a reaction solvent or a solution containing a monomer to cause a polymerization reaction; a solution containing the monomer and a radical initiator A solution containing each of the monomers separately added to a reaction solvent or a solution containing a monomer to cause a polymerization reaction; a plurality of types of solutions containing each monomer; and a solution containing a radical initiator And a method of dropping them into a reaction solvent or a monomer-containing solution to cause a polymerization reaction.
• the reaction temperature in the polymerization is appropriately determined depending on the type of radical initiator, but is usually 30 ° C. to 180 ° C., preferably 40 ° C. to 160 ° C., and more preferably 50 ° C. to 140 ° C.
• the dropping time varies depending on the reaction temperature, the type of radical initiator, the monomer to be reacted, etc., but is usually 30 minutes to 8 hours, preferably 45 minutes to 6 hours, and more preferably 1 hour to 5 hours.
• the total reaction time including the dropping time is usually 30 minutes to 8 hours, preferably 45 minutes to 7 hours, and more preferably 1 hour to 6 hours.
• radical initiator examples include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis ( 2-cyclopropylpropionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobisisobutyrate and the like. These radical initiators can be used in combination of two or more.
• the solvent used for the polymerization is not limited as long as it is a solvent other than a solvent that inhibits polymerization of each monomer and can dissolve the monomer.
• the solvent include alcohol solvents, ketone solvents, amide solvents, ester solvents, lactone solvents, nitrile solvents, and the like. Two or more of these solvents can be used in combination.
• the polymer obtained by the polymerization reaction can be recovered by a reprecipitation method.
• the reprecipitation solvent an alcohol solvent or the like can be used.
• a molecular weight modifier can be used to adjust the molecular weight.
• the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid; dimethyl Xanthogens such as xanthogen sulfide and diisopropylxanthogen disulfide; terpinolene, ⁇ -methylstyrene dimer and the like.
• the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is preferably 1,000 to 20,000, more preferably 2,000 to 15,000.
• Mw weight average molecular weight
• GPC gel permeation chromatography
• the ratio (Mw / Mn) of Mw to polystyrene-reduced number average molecular weight (Mn) by GPC of the [A] polymer is usually from 1 to 5, preferably from 1 to 3, and more preferably from 1 to 2.
• Mw and Mn of the polymer in this specification were measured by GPC under the following conditions.
• the photoresist composition contains a [B] acid generator.
• the acid generator generates an acid by exposure, dissociates the acid dissociable group of the [A] polymer by the acid, and generates a carboxy group or the like. As a result, the polarity of the [A] polymer increases and the [A] polymer in the exposed area becomes soluble in the alkaline developer.
• the form of inclusion of the [B] acid generator in the photoresist composition the form of a compound as described later (hereinafter also referred to as “[B] acid generator” as appropriate) is incorporated as part of the polymer. Either of these forms may be used.
• Examples of the acid generator include onium salt compounds, sulfonimide compounds, halogen-containing compounds, diazoketone compounds, and the like. Of these, onium salt compounds and sulfonimide compounds are preferred.
• onium salt compounds examples include sulfonium salts (including tetrahydrothiophenium salts), iodonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Of these, sulfonium salts and iodonium salts are preferred.
• sulfonium salt examples include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept- 2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro- n-octanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2.
• tetrahydrothiophenium salt examples include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nona.
• iodonium salt examples include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl- 1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t -Butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,
• sulfonimide compound examples include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene -2,3-dicarboximide and the like.
• sulfonium salts having a polycyclic alicyclic hydrocarbon structure such as an adamantyl group are more preferable, and triphenylsulfonium 4- (adamantylcarbonyloxy) -1,1,2-trimethyl is preferred.
• triphenylsulfonium Adamantyloxycarbonyl-1,1-difluoromethanesulfonate is particularly preferred, and triphenylsulfonium 4- (adamantylcarbonyloxy) -1,1,2-trifluorobutanesulfonate is most preferred.
• the content of the acid generator when it is a [B] acid generator is usually from 0 to 100 parts by mass of the [A] polymer from the viewpoint of ensuring the sensitivity and developability as a resist. 1 to 20 parts by mass, preferably 0.5 to 15 parts by mass.
• the content of the acid generator is less than 0.1 parts by mass, the sensitivity and developability of the photoresist composition tend to decrease.
• the content of the [B] acid generator exceeds 20 parts by mass, the transparency to radiation tends to decrease.
• the polymer is a polymer having the structural unit (I) represented by the above formula (1) and containing a fluorine atom.
• the polymer functions as a surface hydrophobizing polymer in the photoresist composition.
• the “surface hydrophobized polymer” refers to a subcomponent polymer having a tendency to be unevenly distributed in the surface layer of a resist film to be formed by being contained in a photoresist composition.
• the photoresist composition contains the [A] polymer and the [C] polymer, the [C] polymer is unevenly distributed when the resist film is formed, and the resist film surface is hydrophobized at the time of exposure. Accordingly, it is possible to perform high-speed scanning or the like in immersion exposure.
• the fluorine atom content of the [C] polymer is preferably higher than that of the [A] polymer.
• the fluorine atom content rate of a [C] polymer is 5 mass% or more, It is more preferable that it is 7 mass% or more, It is further more preferable that it is 10 mass% or more.
• the fluorine atom content of the [A] polymer is preferably less than 5% by mass, more preferably 3% by mass or less, and even more preferably 1% by mass or less.
• the fluorine atom content (% by mass) can be calculated from the polymer structure determined by 13 C-NMR measurement.
• the polymer is a structural unit other than the structural unit (I), for example, other than the structural unit (II) and / or the structural unit (I) containing the acid dissociable group represented by the formula (2). It is preferable to further have a structural unit (IV) containing an alkali dissociable group.
• the [C] polymer is a group consisting of a structural unit containing a fluorine atom other than the structural unit (I) and the structural unit (IV), a lactone structure, a cyclic carbonate structure, and a sultone structure, unless the effects of the present invention are impaired.
• the [C] polymer may have other structural units, such as a structural unit containing the at least 1 sort (s) of structure selected more, and a structural unit containing a polar group.
• the [C] polymer may have 2 or more types of each structural unit.
• each structural unit will be described in detail.
• the structural unit (I) is a structural unit represented by the above formula (1).
• the photoresist composition can form a resist pattern having a small LWR and a good pattern shape.
• the [C] polymer has the specific structure, so that the linking chain of the structural unit (I) is included. The acid or alkali is cleaved to lower the molecular weight, and the solubility in the developer is improved. As a result, it is considered that development defects can be suppressed while improving the receding contact angle on the resist film surface, and a resist pattern having a small LWR and a good shape can be formed.
• R 1 and R 2 are each independently a hydrogen atom, a methyl group or a trifluoromethyl group.
• E 1 and E 2 are each independently an oxygen atom, * 1 —CO—O— or * 1 —CO—NH—.
• * 1 indicates a site bonded to a carbon atom of an adjacent polymer chain.
• A is a divalent group having an acid dissociable group or an alkali dissociable group in the linking chain.
• G is a single bond or a (n + 1) -valent linking group.
• n is an integer of 1 to 3. when n is 2 or more, plural A, E 2 and R 2 may be the same as or different from each other.
• E 1 and E 2 an oxygen atom or * 1 —CO—O— is preferable, and * 1 —CO—O— is more preferable.
• Examples of the acid dissociable group possessed by the divalent group represented by A include the same groups as A 1 in the formula (1-1) described later.
• Examples of the divalent group having an alkali dissociable group represented by A include a group similar to R A in the formula (1-2) described later.
• Examples of A include a group composed only of an acid-dissociable group or an alkali-dissociable group, and a group in which an acid-dissociable group or alkali-dissociable group is bonded to another linking group.
• Examples of other linking groups include those exemplified as G below.
• Examples of the (n + 1) -valent linking group represented by G include a linear or branched hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, and a carbon number of 6 To 30 aromatic hydrocarbon groups or the group consisting of —CO—, —COO—, —OCO—, —O—, —NR—, —CS—, —S—, —SO—, and —SO 2 —. And a group obtained by combining at least one selected group with a hydrocarbon group having 1 to 30 carbon atoms.
• linear or branched hydrocarbon group having 1 to 30 carbon atoms examples include hydrocarbon groups such as methane, ethane, propane, butane, pentane, hexane, heptane, decane, icosane and triacontane (n + 1). And a group excluding individual hydrogen atoms.
• Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms include monocyclic saturated hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, methylcyclohexane, and ethylcyclohexane; Monocyclic unsaturated hydrocarbons such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclopentadiene, cyclohexadiene, cyclooctadiene, cyclodecadiene; Bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 2,6 ] decane, tricyclo [3.3.1.1 3,7 ] decane, Tetracycl
• aromatic hydrocarbon group having 6 to 30 carbon atoms examples include (n + 1) aromatic hydrocarbons such as benzene, naphthalene, phenanthrene, anthracene, tetracene, pentacene, pyrene, picene, toluene, xylene, ethylbenzene, mesitylene, cumene, and the like. ) Groups from which a single hydrogen atom is removed.
• the linking group represented by G may have an acid dissociable group or an alkali dissociable group.
• N is preferably 1 or 2, and more preferably 1.
• the structural unit (I) is preferably represented by the above formula (1-1).
• the structural unit (I) is the specific structural unit, the linking chain is effectively cleaved by the acid generated from the [B] acid generator upon exposure, and the molecular weight of the [C] polymer is reduced. Can do.
• the solubility with respect to the alkali developing solution of the [C] polymer in an exposure part can be improved more, and generation
• R 1 , R 2 , G and n have the same meanings as in formula (1) above.
• a 1 is a divalent acid dissociable group.
• n is 2 or more, the plurality of A 1 and R 2 may be the same or different.
• a 1 is preferably represented by the above formula (2-1), (2-2) or (2-3).
• a 1 is the specific acid dissociable group, the acid dissociation property of A 1 is further increased, development defects can be further suppressed, and a resist pattern having a smaller LWR can be formed.
• R 3 and R 5 are each independently an alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or 6 to 6 carbon atoms. 22 is a monovalent aromatic hydrocarbon group.
• R 4 is an alkanediyl group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 22 carbon atoms.
• any two of R 3 to R 5 may be bonded to each other to form a ring structure together with the carbon atoms to which they are bonded.
• R 6 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or carbon.
• R 7 is a single bond, an alkanediyl group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 22 carbon atoms.
• any two of R 6 to R 8 may be bonded to each other to form a ring structure together with the carbon atom to which R 6 and R 8 are bonded.
• R 9 is an alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a monovalent aromatic carbon group having 6 to 22 carbon atoms. It is a hydrogen group.
• R 10 is a single bond, an alkanediyl group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 22 carbon atoms.
• R 11 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 22 carbon atoms.
• any two of R 9 to R 11 may be bonded to each other to form a ring structure together with the carbon atom to which R 10 and R 11 are bonded.
• ** represents a bonding site with the ester group in the formula (1-1).
• some or all of the hydrogen atoms of R 3 to R 11 may be substituted.
• Examples of the alkyl group having 1 to 4 carbon atoms represented by R 3 , R 5 , R 6 , R 8 , R 9 and R 11 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, Examples thereof include 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 represented by R 3 , R 5 , R 6 , R 8 , R 9 and R 11 include, for example, Monocyclic aliphatic saturated hydrocarbon groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group; A monocyclic aliphatic unsaturated hydrocarbon group such as a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cyclodecenyl group, a cyclododecenyl group, a cyclopentadienyl group, a cyclohexadienyl group, a cyclodecadienyl group; Bicyclo [2.2.1] heptenyl group
• a polycyclic aliphatic saturated hydrocarbon group such as a dodecanyl group or an adamantanyl group
• a polycyclic aliphatic unsaturated hydrocarbon group such as 0 2,7 ] dodecenyl group.
• Examples of the monovalent aromatic hydrocarbon group having 6 to 22 carbon atoms represented by R 3 , R 5 , R 6 , R 8 , R 9 and R 11 include benzyl group, naphthyl group, phenanthryl group, anthryl. Group, tetracenyl group, pentacenyl group, tolyl group, xylyl group, ethylbenzyl group, mesityl group, cumyl group and the like.
• Examples of the alkanediyl group having 1 to 4 carbon atoms represented by R 4 , R 7 and R 10 include, for example, the carbon number represented by the above R 3 , R 5 , R 6 , R 8 , R 9 and R 11. And groups obtained by removing one hydrogen atom from 1 to 4 alkyl groups.
• Examples of the divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R 4 , R 7 and R 10 include, for example, the above R 3 , R 5 , R 6 , R 8 , R 9 and R 11. And a group obtained by removing one hydrogen atom from a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by:
• Examples of the divalent aromatic hydrocarbon group having 6 to 22 carbon atoms represented by R 4 , R 7 and R 10 include, for example, R 3 , R 5 , R 6 , R 8 , R 9 and R 11 . And a group obtained by removing one hydrogen atom from a monovalent aromatic hydrocarbon group having 6 to 22 carbon atoms.
• Examples of the ring structure that any two of R 3 to R 5 may be bonded to each other and formed together with the carbon atom to which they are bonded include, for example, an alicyclic hydrocarbon structure having 4 to 20 carbon atoms, and the like. Can be mentioned. Specifically, a polycyclic alicyclic hydrocarbon structure having a bridged skeleton such as an adamantane skeleton or a norbornane skeleton; a monocyclic alicyclic hydrocarbon having a cycloalkane skeleton such as cyclopentane, cyclohexane or cyclooctane Examples include the structure. In addition, these structures may be substituted with, for example, one or more linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms.
• any two of R 6 to R 8 may be bonded to each other to form a ring structure that may be formed together with the carbon atom to which R 6 and R 8 are bonded; and any two of R 9 to R 11 may be bonded to each other.
• the ring structure that may be formed together with the carbon atom to which R 10 and R 11 are bonded for example, any two of the above R 3 to R 5 are bonded to each other, and the carbon atom to which each is bonded Examples thereof include ring structures similar to those exemplified as the ring structure that may be formed together.
• a heterocyclic structure having 4 to 20 carbon atoms can be mentioned.
• a polycyclic heterocyclic structure having a bridged skeleton such as an adamantane skeleton or norbornane skeleton containing an oxygen atom
• a monocyclic heterocyclic structure having a cycloalkane skeleton such as cyclopentane or cyclohexane containing an oxygen atom Is mentioned.
• these structures may be substituted with, for example, one or more linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms.
• the above A 1 is preferably represented by the above formula (2-1), and any two of R 3 to R 5 in the formula (2-1) are bonded to each other, and the carbon to which they are bonded It is more preferable to form a ring structure with atoms, and this ring structure is particularly preferably a monocyclic alicyclic hydrocarbon structure having a cycloalkane skeleton such as cyclopentane, cyclohexane, cyclooctane or the like.
• G preferably has an acid dissociable group in the linking chain, and preferably has an acid dissociable group represented by the above formulas (2-1) to (2-3). It is more preferable to have an acid dissociable group represented by the above formula (2-1).
• G is preferably an acid dissociable group represented by the above formulas (2-1) to (2-3), and is represented by the above formula (2-1). Particularly preferred is an acid dissociable group.
• the structural unit (I) is preferably represented by the above formula (1-2).
• the structural unit (I) is the specific structural unit, the connecting chain is effectively cleaved by an alkali developer during alkali development, and the molecular weight of the [C] polymer can be reduced. Thereby, the solubility with respect to the alkali developing solution of a [C] polymer can be improved more, generation
• R 1 , R 2 , E 1 , E 2 and n are as defined in the above formula (1).
• R A is a group having an alkali dissociable group in the linking chain.
• Two R 12 s are each independently a single bond, a divalent chain hydrocarbon group having 1 to 10 carbon atoms or a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms.
• R 13 represents a single bond, a (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, or —CO—, —COO—, —OCO—, —O—, —NR—, —CS—, —S—.
• —SO—, and —SO 2 — are groups obtained by combining at least one group selected from the group consisting of —SO 2 — and a hydrocarbon group having 1 to 20 carbon atoms.
• R 14 is a divalent hydrocarbon group having 1 to 20 carbon atoms.
• Two X 0 s are each independently a single bond or a divalent chain hydrocarbon group having 1 to 20 carbon atoms in which some or all of the hydrogen atoms are substituted with fluorine atoms.
• n is 2 or more, the plurality of R 12 , X 0 , R A , R 14 , E 2 and R 2 may be the same or different.
• Examples of the (n + 1) valent hydrocarbon group having 1 to 20 carbon atoms include linear or branched chain hydrocarbon groups, alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. An aromatic hydrocarbon group is mentioned.
• linear or branched hydrocarbon group having 1 to 20 carbon atoms examples include hydrocarbon groups such as methane, ethane, propane, butane, pentane, hexane, heptane, decane, icosane and triacontane (n + 1) And a group excluding individual hydrogen atoms.
• Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic saturated hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, methylcyclohexane, and ethylcyclohexane; Monocyclic unsaturated hydrocarbons such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclopentadiene, cyclohexadiene, cyclooctadiene, cyclodecadiene; Bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 2,6 ] decane, tricyclo [3.3.1.1 3,7 ] decane, Tetracycl
• aromatic hydrocarbon group having 6 to 20 carbon atoms examples include aromatic hydrocarbon groups such as benzene, naphthalene, phenanthrene, anthracene, tetracene, pentacene, pyrene, picene, toluene, xylene, ethylbenzene, mesitylene, cumene ( a group excluding n + 1) hydrogen atoms.
• the group having an alkali dissociable group represented by R A is not particularly limited, but is preferably a group represented by the above formula (1-3).
• RA alkali dissociation property of RA is further increased, the solubility of [C] polymer in an alkaline developer can be further improved, and the occurrence of development defects can be further suppressed.
• a resist pattern having a smaller LWR and a good pattern shape can be formed.
• R 15 is a divalent hydrocarbon group which may have a fluorine atom.
• the two Y 0 are each independently —O—, * 2 —O—CO—, * 2 —CO—O—, * 2 —SO 2 —O—. * 2 indicates the site for binding to X 0.
• divalent hydrocarbon groups optionally having a fluorine atom represented by R 15
• examples of the divalent hydrocarbon group include a divalent chain hydrocarbon group and a divalent alicyclic group.
• a hydrocarbon group, a divalent aromatic hydrocarbon group, etc. are mentioned.
• divalent chain hydrocarbon group examples include a methanediyl group, an ethanediyl group, a propanediyl group, and a butanediyl group. Of these, ethanediyl group and butanediyl group are preferable.
• divalent alicyclic hydrocarbon group examples include a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, a norbornanediyl group, and an adamantanediyl group.
• divalent aromatic hydrocarbon group examples include phenylene group, benzylene group, phenethylene group, phenylenepropylene group, naphthylene group, naphthylene methylene group and the like.
• R 15 is preferably a divalent chain hydrocarbon group which may have a fluorine atom, more preferably an ethanediyl group or a 2,2,3,3-tetrafluorobutanediyl group.
• Y 0 is preferably * 2 —CO—O—. However, * 2 shows a site that binds to the X 0.
• Examples of the divalent chain hydrocarbon group having 1 to 10 carbon atoms represented by R 12 include the same groups as the divalent chain hydrocarbon group exemplified for R 15 .
• Examples of the divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R 12 include the same groups as the divalent alicyclic hydrocarbon group exemplified for R 15 .
• R 12 is preferably a divalent chain hydrocarbon group having 1 to 10 carbon atoms, and more preferably a propanediyl group.
• Examples of the (n + 1) -valent hydrocarbon group having 1 to 20 carbon atoms represented by R 13 include, for example, by removing (n-1) hydrogen atoms from the divalent hydrocarbon group exemplified as R 15 above. And the like.
• R 13 is preferably a single bond.
• Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R 14 include the same groups as the divalent hydrocarbon group exemplified as R 15 .
• R 14 is preferably a single bond.
• Examples of the divalent chain hydrocarbon group having 1 to 20 carbon atoms in which some or all of the hydrogen atoms represented by X 0 are substituted with fluorine atoms include those represented by the following formula (X 0 -1): Can be mentioned.
• R f is independently of each other a fluorine atom or a perfluoroalkyl group having 1 to 10 carbon atoms.
• P is preferably 1 or 2, and more preferably 1.
• R f is preferably a trifluoromethyl group or a fluorine atom, and more preferably a fluorine atom.
• X 0 is preferably a difluoromethanediyl group.
• structural unit (I) examples include structural units represented by the following formulas (I-1) to (I-9) (hereinafter also referred to as “structural units (I-1) to (I-9)”), etc. Is mentioned.
• R ⁇ 1 > and R ⁇ 2 > are synonymous with the said Formula (1).
• structural units (I-1) to (I-5) are preferred.
• the content ratio of the structural unit (I) in the polymer is preferably 3 mol% or more and 40 mol% or less, and preferably 5 mol% or more and 30 mol% with respect to all the structural units constituting the [C] polymer.
• the following is more preferable, and 7 mol% or more and 20 mol% or less is particularly preferable.
• Examples of the monomer that gives the structural unit (I) include a monomer represented by the following formula.
• the polymer preferably further has a structural unit containing an acid-dissociable group other than the structural unit (I).
• the structural unit containing an acid dissociable group the structural unit (II) in the [A] polymer is preferable.
• the structural unit (IV) is a structural unit other than the structural unit (I) and includes an alkali dissociable group.
• the structural unit (IV) includes a structural unit represented by the following formula (IV-1) (hereinafter also referred to as “structural unit (IV-1)”), and a structural unit represented by the following formula (IV-2): (Hereinafter also referred to as “structural unit (IV-2)”) is preferred.
• R 20 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
• k is an integer of 1 to 3.
• R 21 is a (k + 1) -valent linking group.
• X 1 is a divalent linking group having a fluorine atom.
• R 22 is a monovalent linear or branched hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a fluorine atom. However, when k is 2 or 3, the plurality of X 1 and R 22 may be the same or different.
• R 23 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
• R 24 is a linking group having no (m + 1) valent fluorine atom.
• m is an integer of 1 to 3.
• a 2 is —COO—.
• R 25 is a hydrocarbon group containing at least one fluorine atom.
• Examples of the (k + 1) -valent linking group represented by R 21 include a linear or branched hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, and a carbon number.
• linear or branched hydrocarbon group having 1 to 30 carbon atoms examples include hydrocarbon groups such as methane, ethane, propane, butane, pentane, hexane, heptane, decane, icosane and triacontane (k + 1). And a group excluding individual hydrogen atoms.
• Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms include monocyclic saturated hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, methylcyclohexane, and ethylcyclohexane; Monocyclic unsaturated hydrocarbons such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclopentadiene, cyclohexadiene, cyclooctadiene, cyclodecadiene; Bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 2,6 ] decane, tricyclo [3.3.1.1 3,7 ] decane, Tetracycl
• aromatic hydrocarbon group having 6 to 30 carbon atoms examples include aromatic hydrocarbon groups such as benzene, naphthalene, phenanthrene, anthracene, tetracene, pentacene, pyrene, picene, toluene, xylene, ethylbenzene, mesitylene, cumene ( and groups excluding k + 1) hydrogen atoms.
• Examples of the divalent linking group having a fluorine atom represented by X 1 include a divalent linear hydrocarbon group having 1 to 20 carbon atoms having a fluorine atom, and a carbon number having a fluorine atom containing a carbonyl group. Examples thereof include 1 to 20 divalent linear hydrocarbon groups. Examples of the C 1-20 divalent linear hydrocarbon group having a fluorine atom include groups represented by the following formulas (X 1 -1) to (X 1 -7).
• X 1 is preferably a group represented by the above formula (X 1 -7).
• Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms which may have a fluorine atom represented by R 22 include alkyl groups such as a methyl group and an ethyl group; Examples thereof include a fluorinated alkyl group having 1 to 20 carbon atoms such as a fluoroethyl group.
• Examples of the structural unit (IV-1) include structural units represented by the following formulas (IV-1a) and (IV-1b).
• R 20 has the same meaning as in the above formula (IV-1).
• Examples of the linking group having no (m + 1) -valent fluorine atom represented by R 24 include a linear or branched hydrocarbon group having 1 to 30 carbon atoms and an alicyclic group having 3 to 30 carbon atoms.
• Examples of the hydrocarbon group containing at least one fluorine atom represented by R 25 include a fluorinated alkyl group containing at least one fluorine atom.
• Examples of the structural unit (IV-2) include a structural unit represented by the following formula (IV-2a).
• R 23 has the same meaning as in the above formula (IV-2).
• structural unit (IV) structural units represented by the above formulas (IV-1a), (IV-1b) and (IV-2a) are preferable.
• the content of the structural unit (IV) in the polymer is preferably 0 mol% or more and 80 mol% or less, more preferably 20 mol% or more and 75 mol% or less, and particularly preferably 30 mol% or more and 70 mol% or less. preferable.
• the polymer is further selected from the group consisting of structural unit (I), a structural unit containing a fluorine atom other than structural unit (IV), a lactone structure, a cyclic carbonate structure, and a sultone structure as another structural unit. You may have a structural unit containing at least 1 type of structure, and a structural unit containing a polar group.
• Monomers that give structural units containing fluorine atoms other than structural unit (I) and structural unit (IV) include 2- (1,1,1,3,3,3-hexafluoro) propyl (meth) acrylate Is preferred.
• the structural unit (III) in the [A] polymer is preferred.
• the polar group a carboxy group and a hydroxy group are preferable.
• the content of the [C] polymer is preferably 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the [A] polymer.
• the polymer can be synthesized, for example, by polymerizing a monomer that gives each predetermined structural unit in a suitable solvent using a radical polymerization initiator.
• 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; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; Halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene; 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-p
• the reaction temperature in the above polymerization is usually 40 ° C to 150 ° C, preferably 50 ° C to 120 ° C.
• the reaction time is usually 1 hour to 48 hours, preferably 1 hour to 24 hours.
• the Mw of the [C] polymer is preferably 1,000 to 20,000, more preferably 2,000 to 10,000, and particularly preferably 3,000 to 9,000.
• Mw of the polymer is less than 1,000, there is a tendency that a sufficient receding contact angle cannot be obtained.
• Mw of the [C] polymer exceeds 20,000, the developability when used as a resist tends to be lowered.
• the ratio (Mw / Mn) of Mw of the polymer to the number average molecular weight (Mn) in terms of polystyrene by GPC method is usually 1 to 5, preferably 1 to 3, and more preferably 1 to 2.
• the photoresist composition preferably contains a [D] acid diffusion controller.
• [D] The acid diffusion controller controls the diffusion phenomenon in the resist film of the acid generated from the [B] acid generator by exposure, and has an effect of suppressing an undesirable chemical reaction in the non-exposed region.
• the photoresist composition further contains a [D] acid diffusion controller, the photoresist composition can form a resist pattern that is more excellent in pattern developability and LWR performance.
• a compound form as described later hereinafter also referred to as “[D] acid diffusion controller” as appropriate
• Examples of the acid diffusion controller include Nt-alkoxycarbonyl group-containing amino compounds, tertiary amine compounds, quaternary ammonium hydroxide compounds, and the like.
• Nt-alkoxycarbonyl group-containing amino compound examples include Nt-butoxycarbonyldi-n-octylamine, Nt-amyloxycarbonyldi-n-octylamine, and Nt-butoxycarbonyldi- n-nonylamine, Nt-amyloxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt-amyloxycarbonyldi-n-decylamine, Nt-butoxycarbonyldicyclohexylamine Nt-amyloxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-amyloxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, N- t-Amyloxycarbonyl-2-adamadama Tylamine, Nt-
• tertiary amine compound examples include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, and tri-n-octyl.
• Tri (cyclo) alkylamines such as amine, cyclohexyldimethylamine, dicyclohexylmethylamine, and tricyclohexylamine; Fragrances such as aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 2,6-dimethylaniline, 2,6-diisopropylaniline Group amines; Alkanolamines such as triethanolamine, N, N-di (hydroxyethyl) aniline; N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, 1,3-bis [1- (4-aminophenyl) -1- Methylethyl] benzenetetramethylenediamine, bis (2-dimethylaminoethyl) ether, bis (2-dieth
• Examples of the quaternary ammonium hydroxide compound include tetra-n-propylammonium hydroxide and tetra-n-butylammonium hydroxide.
• an onium salt compound which is decomposed by exposure and loses basicity as acid diffusion controllability can be used.
• an onium salt compound include a sulfonium salt compound represented by the following formula (5-1), an iodonium salt compound represented by the formula (5-2), and the like.
• R 26 to R 30 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a halogen atom.
• Anb ⁇ is OH ⁇ , R 31 —COO ⁇ , R 31 —SO 3 ⁇ , or an anion represented by the following formula (6).
• R 31 is each independently an alkyl group, an aryl group or an alkanol group.
• Examples of the sulfonium salt compound and the iodonium salt compound include triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylsulfonium hydroxide, diphenyl-4-hydroxyphenylsulfonium acetate, and diphenyl.
• the content when the acid diffusion controller is a [D] acid diffusion controller is preferably 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymer [A]. 0.4 to 15 parts by mass is more preferable. [D] By making content of an acid diffusion control agent into the said range, the pattern developability and LWR performance of the said photoresist composition improve more.
• the photoresist composition usually contains an [E] solvent.
• the solvent a solvent that can uniformly dissolve or disperse each component and does not react with each component is preferably used.
• Examples of the solvent include alcohols, ethers, ketones, amides, esters, hydrocarbons and the like. In addition, these solvents can use 2 or more types together.
• alcohols include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec -Pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-he Mono
• ethers examples include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, methoxybenzene and the like.
• ketones include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, and methyl-n-hexyl.
• ketones di-iso-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, and the like.
• amides include N, N′-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N -Methylpropionamide, N-methylpyrrolidone and the like.
• esters examples include methyl acetate, ethyl acetate, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, and 3-acetate acetate.
• hydrocarbons examples include n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, cyclohexane, Aliphatic hydrocarbons such as methylcyclohexane; Fragrances such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, iso-propylbenzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di-iso-propylbenzene, n-amylnaphthalene Group hydrocarbons, etc.
• esters and ketones are preferable, and propylene glycol monomethyl ether acetate, cyclohexanone, and ⁇ -butyrolactone are more preferable.
• the photoresist composition may contain a surfactant, a sensitizer, and the like as other optional components.
• the said photoresist composition may contain 2 or more types of said other arbitrary components.
• Surfactants have the effect of improving coatability, striation, developability, and the like.
• the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol diacrylate.
• Nonionic surfactants such as stearate are listed.
• Examples of commercially available products include KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no.
• the sensitizer exhibits the effect of increasing the amount of [B] acid generators produced, and has the effect of improving the “apparent sensitivity” of the photoresist composition.
• the sensitizer include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines and the like.
• the photoresist composition contains, for example, an [A] polymer, a [B] acid generator, a [C] polymer, and a [D] acid diffusion control agent and other optional components in a [E] solvent. It is prepared by mixing at a predetermined ratio. In use, the photoresist composition is usually dissolved in a solvent such that the total solid content is usually 1% by mass to 30% by mass, preferably 1.5% by mass to 25% by mass, and then, for example, the pore diameter is about 200 nm. It is prepared by filtering with a filter.
• the resist pattern forming method of the present invention comprises: A step of forming a resist film on a substrate using the photoresist composition (hereinafter, also referred to as “resist film forming step”), A step of exposing the resist film (hereinafter also referred to as “exposure step”) and a step of developing the exposed resist film (hereinafter also referred to as “development step”).
• resist film forming step A step of forming a resist film on a substrate using the photoresist composition
• exposure step A step of exposing the resist film
• development step a step of developing the exposed resist film
• a resist film is formed on the substrate using the photoresist composition.
• the substrate for example, a conventionally known substrate such as a silicon wafer or a wafer coated with aluminum can be used.
• an organic or inorganic lower antireflection film disclosed in Japanese Patent Publication No. 6-12452 and Japanese Patent Application Laid-Open No. 59-93448 may be formed on the substrate.
• the film thickness of the resist film to be formed is usually 10 nm to 1,000 nm, and preferably 10 nm to 500 nm.
• the solvent in the coating film may be volatilized by pre-baking (PB).
• PB pre-baking
• the temperature condition of PB is appropriately selected depending on the composition of the photoresist composition, but is usually about 30 ° C. to 200 ° C., preferably 50 ° C. to 150 ° C.
• Exposure process In this step, exposure is performed by reducing and projecting a desired pattern of the resist film formed in the resist film forming step through a mask having a specific pattern and, if necessary, an immersion liquid.
• an isotrench pattern can be formed by performing reduced projection exposure on a desired region through an isoline pattern mask.
• the immersion liquid used for exposure include water and a fluorine-based inert liquid.
• the immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient that is as small as possible so as to minimize distortion of the optical image projected onto the film.
• the exposure light is ArF excimer laser light (wavelength 193 nm)
• water is preferable from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.
• an additive that decreases the surface tension of water and increases the surface activity may be added in a small proportion.
• This additive is preferably one that does not dissolve the resist layer on the wafer and can ignore the influence on the optical coating on the lower surface of the lens.
• the water used is preferably distilled water.
• the exposure light used for exposure is appropriately selected according to the type of [B] acid generator, and examples thereof include ultraviolet rays, far ultraviolet rays, EUV (ultra-ultraviolet rays), X-rays, and charged particle beams. Of these, far ultraviolet rays such as ArF excimer laser light and KrF excimer laser light (wavelength 248 nm) are preferable, and ArF excimer laser light is more preferable.
• the exposure conditions such as the exposure amount are appropriately selected according to the composition of the photoresist composition and the type of additive.
• PEB post-exposure baking
• the dissociation reaction of the acid dissociable group in the photoresist composition can proceed smoothly.
• PEB temperature it is 30 degreeC or more and less than 200 degreeC normally, and 50 degreeC or more and less than 150 degreeC are preferable.
• the dissociation reaction may not proceed smoothly.
• the acid generated from the [B] acid generator diffuses widely to the unexposed area and is good. There is a possibility that a pattern cannot be obtained.
• a developing method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is allowed to stand for a certain time (a paddle method) ), A method of spraying the developer on the substrate surface (spray method), a method of continuously applying the developer while scanning the developer coating nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc.
• dip method a method in which a substrate is immersed in a tank filled with a developer for a certain time
• a paddle method a method in which the developer is raised on the surface of the substrate by surface tension and is allowed to stand for a certain time
• a method of spraying the developer on the substrate surface spray method
• a method of continuously applying the developer while scanning the developer coating nozzle on the substrate rotating at a constant speed dynamic dispensing method
• the polymer of the present invention has a fluorine atom and the structural unit (I) represented by the above formula (1), it can be suitably used as a component of the photoresist composition of the present invention.
• the said monomer solution was dripped there over 4 hours, and also it age
• the polymerization solution was cooled with water and cooled to 30 ° C. or lower.
• the polymerization solution was concentrated under reduced pressure using an evaporator until the weight of the polymerization solution reached 200 g. Thereafter, the polymerization solution was put into 1,000 g of methanol, and reprecipitation operation was performed. The precipitated slurry was filtered by suction, and the solid content was washed with methanol three times. This solid content was vacuum dried at 60 ° C.
• Example 2 to 16 and Synthesis Examples 2 and 3 Each polymer was synthesized in the same manner as in Example 1 except that the types and amounts of compounds (monomers) shown in Table 2 were used. Table 2 also shows the yield (%), Mw, and Mw / Mn of each synthesized polymer. In Table 2, “-” indicates that the corresponding compound was not used.
• D-1 Compound represented by the following formula (D-1)
• D-2 Compound represented by the following formula (D-2)
• D-3 Compound represented by the following formula (D-3)
• [Example 17] [A] 100 parts by mass of (A-1) as a polymer, [B] 10 parts by mass of (B-1) as an acid generator, [C] 3 parts by mass of (C-1) as a polymer, D] 7 parts by mass of (D-1) as an acid diffusion controlling agent, and (E-1) 1, 732.5 parts by mass, (E-2) 742.5 parts by mass and (E -3) 275 parts by mass were mixed to prepare a photoresist composition.
• Example 18 to 37 and Comparative Examples 1 and 2 Each photoresist composition was prepared in the same manner as in Example 17 except that the components having the types and contents shown in Table 3 were used.
• a film having a thickness of 80 nm was formed on an 8-inch silicon wafer using a photoresist composition, and soft baking (SB) was performed at 120 ° C. for 60 seconds. Then, the receding contact angle of the formed film was measured in the following procedure using DSA-10 manufactured by KRUS under an environment of room temperature 23 ° C., humidity 45%, and normal pressure.
• the developer dissolution rate measurement sample was spin-coated on an 8-inch silicon wafer on which an underlayer antireflection film (manufactured by Nissan Chemical Co., ARC29A) was formed, using the trade name “CLEAN TRACK ACT8”, and heated at 120 ° C. for 60 seconds.
• an underlayer antireflection film manufactured by Nissan Chemical Co., ARC29A
• a coating film having a thickness of 200 nm was formed.
• this coating film was irradiated with an excimer laser having a wavelength of 193 nm using an ArF excimer laser exposure apparatus (manufactured by NIKON, NSR S306C, numerical aperture 0.78) at 60 mJ / cm 2 , and then heated at 100 ° C. for 60 seconds. did.
• the thickness (film thickness) of the coating film was measured by a trade name “Lambda Ace VM2010” (Dainippon Screen). Thereafter, the dissolution rate in a developing solution (2.38% TMAH (tetramethylammonium hydroxide) aqueous solution) was measured using a trade name “Resist Development Analyzer MODEL RDA-808R8”. When this dissolution rate was 1,000 nm / sec or more, the dissolution rate was “A”, and when it was less than 1,000 nm / sec, “B”.
• TMAH tetramethylammonium hydroxide
• PEB was performed at 100 ° C. for 60 seconds. Thereafter, development was performed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 30 seconds using a GP nozzle of a developing device of Clean Electron “ACT12” manufactured by Tokyo Electron, rinsed with pure water for 7 seconds, and shaken off at 3,000 rpm. It was dried to form a positive resist pattern.
• the exposure amount for forming 1 L / 1S having a width of 45 nm was determined as the optimum exposure amount. With this optimum exposure amount, 1L / 1S having a line width of 45 nm was formed on the entire surface of the wafer to obtain a defect inspection wafer.
• the number of defects on the defect inspection wafer was measured using KLA2810 manufactured by KLA-Tencor. Furthermore, the defects measured by the KLA2810 were classified into those judged to be derived from the resist film and those derived from the outside. After classification, the total number of defects determined to be derived from the resist film was defined as development defect evaluation. When the total number of defects was less than 1,000 / wafer, the development defect evaluation was “A”, and when it was 1,000 or more, “B”.
• a 110 nm-thick film was formed from a photoresist composition on a 12-inch silicon wafer on which the lower antireflection film was formed, and soft baking (SB) was performed at 120 ° C. for 60 seconds.
• the cross-sectional shape of the formed pattern was observed with a scanning electron microscope (2) (trade name: “S-4800”, manufactured by Hitachi High-Technologies Corporation), and the line width of the line portion at the intermediate portion in the thickness direction of the film Lb and the line width La on the coating surface were measured. Thereafter, the formula: (La ⁇ Lb) / Lb is calculated, and when the calculated value is 0.90 ⁇ (La ⁇ Lb), “T-top” is set, and (La ⁇ Lb) ⁇ 1.1. In this case, the top round was selected. When 0.90 ⁇ (La ⁇ Lb) ⁇ 1.1, “A” was set. In addition, when the unmelted portion was generated in the exposed portion, it was set as “B”.
• LWR (nm) A positive resist pattern was formed by the same method as in the development defect evaluation, and the optimum exposure (Eop) was measured.
• the 3-sigma value (variation) of the measured line width was defined as LWR (nm).
• the polymer of the present invention was superior in solubility in the developer compared to the comparative example. Further, as is clear from the results in Table 3, the photoresist composition of the present invention can suppress the occurrence of development defects while improving the receding contact angle on the resist film surface as compared with the comparative example. In addition, it was found that a resist pattern having a small LWR and a good shape can be formed.
• the photoresist composition, resist pattern forming method and polymer of the present invention in the immersion exposure process, the receding contact angle of the resist film surface during exposure can be improved, and receding contact during alkali development. As a result, it is possible to greatly reduce the corners, thereby suppressing development defects and forming a resist pattern having a small LWR and a good pattern shape. Therefore, the photoresist composition, resist pattern forming method, and polymer can be suitably used in a lithography process that requires further miniaturization.

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• 2013
  • 2013-03-19 WO PCT/JP2013/057913 patent/WO2013141265A1/fr not_active Ceased
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