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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
  • C08F212/22—Oxygen
  • C08F212/24—Phenols or alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
• • 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
  • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
  • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • 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
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • 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
• • 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
  • G03F7/20—Exposure; Apparatus therefor
• • 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
  • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
  • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light

Definitions

• the present disclosure relates to a radiation-sensitive composition and a resist pattern forming method.
• the radiation-sensitive composition is irradiated with far-ultraviolet rays such as ArF excima laser, extreme ultraviolet rays (EUV), electron beams, and the like.
• far-ultraviolet rays such as ArF excima laser, extreme ultraviolet rays (EUV), electron beams, and the like.
• EUV extreme ultraviolet rays
• an acid is generated in the exposed part, and the chemical reaction involving the generated acid causes a difference in the dissolution rate in the developing solution between the exposed part and the unexposed part, thereby forming a resist pattern on the substrate. ..
• Patent Document 1 proposes a chemically amplified resist composition containing an acid generator having a triarylsulfonium cation having one or more fluorine atoms and a resin having a repeating unit having a phenolic hydroxyl group. ..
• the resist pattern has been rapidly miniaturized, and attempts have been made to form a pattern having a line width of 40 nm or less, for example. Even when forming such a fine resist pattern, it is required to form a good resist pattern with a small exposure amount (that is, with high sensitivity).
• the radiation-sensitive composition used in the lithography process has a small CDU (Critical Dimensions Uniformity) in forming a hole pattern, and the difference in dissolution rate between the exposed portion and the unexposed portion with respect to the developing solution is sufficiently large for development. Characteristics such as low residue are required.
• the present disclosure has been made in view of the above problems, and an object thereof is a radiation-sensitive composition and a resist pattern capable of forming a resist pattern having high sensitivity, small CDU, and suppressed development defects.
• the purpose is to provide a forming method.
• a polymer (A) containing a structural unit having a hydroxyl group bonded to an aromatic ring and an acid-generating compound having a radiation-sensitive onium cation structure and an organic anion structure (however, the polymer (A) is excluded. ) And one or more compounds selected from the group consisting of the polymer (A) and the acid-generating compound, the fluoroalkyl group and the fluoro group (excluding the fluoro group in the fluoroalkyl group).
• the radiation-sensitive composition and the resist pattern forming method of the present disclosure since the sensitivity is high, a good resist pattern can be formed with a small exposure amount. Further, it is possible to form a resist pattern having a small CDU and few development defects.
• the radiation-sensitive composition of the present disclosure contains (A) a structural unit having a hydroxyl group bonded to an aromatic ring (hereinafter, also referred to as “structural unit (I)”). It is a polymer composition containing a coalescence and an acid-generating compound having a radiation-sensitive onium cation structure and an organic anion structure (however, excluding the polymer (A)).
• structural unit (I) a structural unit having a hydroxyl group bonded to an aromatic ring
• structural unit (I) is a polymer composition containing a coalescence and an acid-generating compound having a radiation-sensitive onium cation structure and an organic anion structure (however, excluding the polymer (A)).
• one or more compounds selected from the group consisting of (A) polymer and acid generating compound are composed of a fluoroalkyl group and a fluoro group (however, the fluoro group in the fluoroalkyl group is excluded).
• a radiosensitive onium cation structure [X] having two or more of at least one substituent ⁇ selected from the group (hereinafter, also referred to as “specific cation structure [X]”) and an organic anion structure having an iodo group [ Y] (hereinafter, also referred to as “specific anion structure [Y]”) is contained in the same compound or different compounds.
• the acid-generating compound contained in the present composition typically has a radiation-sensitive onium cation structure and an organic anion structure which is a conjugate base of the acid (hereinafter, also simply referred to as an organic anion structure) as a structure for generating an acid. It is a compound having a structure derived from an onium salt having and.
• the organic anion is usually an anion obtained by removing protons from the acid group of an organic acid.
• the radiation-sensitive onium cation is decomposed by the action of radiation to release the organic anion, and the released organic anion is extracted from the components contained in the composition (for example, the acid-generating compound itself or the solvent).
• an acid is given to the components contained in the composition.
• the acid generating compound contained in the present composition include (B) an acid generating agent and (C) an acid diffusion controlling agent.
• the acid-generating compound contained in the present composition may be one kind or two or more kinds.
• the polymer contained in this composition is classified as "(A) polymer” as long as it has the structural unit (I). Therefore, when the polymer contained in the present composition has a radiation-sensitive onium cation structure and an organic anion structure together with the structural unit (I), the polymer corresponds to "(A) polymer". That is, in the present specification, the "acid-generating compound” is distinguished from the polymer (A) in that it does not have the structural unit (I).
• the specific cation structure [X] may be contained in the polymer (A) or the acid-generating compound. Further, both the polymer (A) and the acid-generating compound may have a specific cationic structure [X].
• the acid generating compound has a specific cation structure [X]
• the acid generator may have a specific cation structure [X]
• the acid diffusion control agent has a specific cation structure [X]. You may have.
• the component having the specific cation structure [X] may be only one kind or two or more kinds. That is, only one of the components contained in the present composition may have a specific cation structure [X], and two or more (for example, (A) polymer and (B) acid generator) are specified. It may have a cationic structure [X].
• the specific cation structure [X] may be a radiation-sensitive onium cation structure possessed by the polymer, or may be a radiation-sensitive onium cation structure possessed by a compound different from the polymer (that is, a low molecular weight compound). Further, the specific cation structure [X] may constitute a radiation-sensitive onium cation structure in both the polymer and the small molecule compound. Therefore, when the acid-generating compound has the specific cation structure [X], the acid-generating compound having the specific cation structure [X] may be a polymer having no structural unit (I) and is a small molecule compound. You may.
• a "small molecule compound” is a compound other than a polymer, that is, a compound having no repeating unit.
• the specific anion structure [Y] may be contained in the polymer (A) or the acid-generating compound. In this case, both the polymer (A) and the acid-generating compound may have a specific anion structure [Y].
• the acid generating compound has a specific anion structure [Y]
• the acid generating agent may have a specific anion structure [Y]
• the acid diffusion controlling agent has a specific anion structure [Y]. You may have.
• the component having the specific anion structure [Y] may be only one kind or two or more kinds. That is, only one of the components contained in the present composition may have a specific anion structure [Y], and two or more (for example, (A) polymer and (B) acid generator) are specified. It may have an anion structure [Y].
• the specific anion structure [Y] may be an anion structure possessed by a polymer or an anion structure possessed by a small molecule compound). Further, the specific anion structure [Y] may constitute an organic anion structure in both the polymer and the small molecule compound. Therefore, when the acid-generating compound has a specific anion structure [Y], the acid-generating compound having the specific anion structure [Y] may be a polymer having no structural unit (I) and is a small molecule compound. You may.
• the present composition comprises a specific cation structure [X] and a specific anion structure [Y] in the same or different compounds in one or more compounds selected from the group consisting of (A) polymers and acid-generating compounds.
• the embodiment is not particularly limited.
• Specific embodiments of the present composition include, for example, (1) a embodiment containing a compound having a specific cation structure [X] and a specific anion structure [Y] in the same molecule; (2) a specific cation structure [X]. Examples thereof include a compound having a specific anion structure [Y] and not having a specific anion structure [Y] and a compound having a specific anion structure [Y] and not having a specific cation structure [X].
• each compound may be a polymer or a small molecule compound. Further, each compound may be contained in the present composition by only one kind, or may be contained in combination of two or more kinds. Furthermore, the present composition may further contain a compound having neither the specific cation structure [X] nor the specific anion structure [Y] as the acid generating compound.
• compositions of the present composition containing the specific cation structure [X] and the specific anion structure [Y] together with the polymer (A) having the structural unit (I) include, for example, the following ⁇ 1> to ⁇ . 10> is mentioned.
• the polymer contains (A) a polymer, (B) an acid generator, and (D) a solvent, and the (A) polymer has a specific cation structure [X] and an organic anion structure having no iodo group (hereinafter, A first polymer having a structural unit derived from a monomer having a "other organic anion structure”) and a radiosensitive onium having only one substituent ⁇ or no substituent ⁇ .
• An embodiment containing a second polymer having a structural unit derived from a monomer having a cation structure hereinafter, also referred to as “another organic cation structure” and a specific anion structure [Y].
• a specific cation structure [X] and a specific anion structure [Y] are contained in the same molecule as the (B) acid generator, which comprises (A) a polymer, (B) an acid generator and (D) a solvent. Or an embodiment containing an onium salt contained in a different molecule.
• ⁇ 4> Contains (A) polymer, (B) acid generator, (C) acid diffusion inhibitor and (D) solvent, and as (C) acid diffusion inhibitor, specific cation structure [X] and specific anion.
• An embodiment comprising a polymer having a derived structural unit and containing an onium salt containing (B) an acid generator containing another organic cation structure and a specific anion structure [Y].
• ⁇ 6> A monomer containing (A) a polymer, (B) an acid generator and (D) a solvent, and having another organic cation structure and a specific anion structure [Y] as the (A) polymer.
• An embodiment comprising a polymer having a derived structural unit and containing an onium salt containing the specific cation structure [X] and another organic anion structure as the (B) acid generator.
• the polymer contains (A) a polymer, (B) an acid generator, (C) an acid diffusion inhibitor, and (D) a solvent, and the (A) polymer has another organic cation structure and a specific anion structure [Y]. ], And contains an onium salt containing a specific cation structure [X] and another organic anion structure as the (C) acid diffusion inhibitor.
• ⁇ 9> Contains (A) polymer, (B) acid generator, (C) acid diffusion inhibitor and (D) solvent, and as (B) acid generator, specific cation structure [X] and other organic substances.
• the embodiments ⁇ 1> to ⁇ 3>, ⁇ 5> to ⁇ 7>, and ⁇ 9> are preferable in that the sensitivity and CDU performance of the present composition can be improved and the development residue is small.
• the embodiments of 1>, ⁇ 3>, ⁇ 6>, ⁇ 7>, and ⁇ 9> are particularly preferable.
• the structural unit (I) is a structural unit having a hydroxyl group bonded to an aromatic ring.
• the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring and the like. Of these, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable.
• the number of hydroxyl groups bonded to the aromatic ring is not particularly limited, but is preferably 1 to 3, and more preferably 1 or 2.
• Examples of the structural unit (I) include a structural unit represented by the following formula (i).
• R 1 is a hydrogen atom, a fluoro group, a methyl group or a trifluoromethyl group.
• L 2 is a single bond, —O—, ⁇ CO ⁇ , —COO ⁇ or —CONH—.
• Y 1 is a monovalent group having a hydroxyl group bonded to an aromatic ring.
• R 1 is preferably a hydrogen atom or a methyl group from the viewpoint of copolymerizability of the monomer giving the structural unit (I).
• L 2 is preferably single bond or -COO-.
• structural unit (I) examples include structural units represented by the following equations (1-1) to (1-12).
• R 1 is a hydrogen atom, a fluoro group, a methyl group or a trifluoromethyl group.
• the specific cation structure [X] is not particularly limited as long as it has a radiation-sensitive onium cation structure having two or more substituents ⁇ .
• the specific cation structure [X] preferably has a sulfonium cation structure or an iodonium cation structure.
• the number of substituents ⁇ of the specific cation structure [X] is preferably 3 or more, preferably 4 or more, in that the sensitivity can be increased while maintaining the CDU performance of the present composition and the dissolution contrast with respect to the developing solution. The above is more preferable.
• the number of substituents ⁇ contained in the specific cation structure [X] is preferably 10 or less, more preferably 8 or less, and 7 or less. More preferably, 6 or less is even more preferable.
• the substituent ⁇ is preferably at least one group selected from the group consisting of a fluoro group bonded to an aromatic ring and a fluoroalkyl group, and a fluoro group bonded to the aromatic ring is more preferable.
• the number of fluoroalkyl groups in the specific cation structure [X] is the number of the substituent ⁇ of the specific cation structure [X]. .. Therefore, for example, when the specific cation structure [X] has two trifluoromethyl groups ( ⁇ CF 3 ), the number of substituents ⁇ of the specific cation structure [X] is two. When the specific cation structure [X] has one fluoro group (-F) and two trifluoromethyl groups (-CF 3 ) bonded to the aromatic ring, the substituent of the specific cation structure [X]. The number of ⁇ is three.
• the binding position of the substituent ⁇ in the specific cation structure [X] is not particularly limited. It is preferable that at least one of the substituents ⁇ of the specific cation structure [X] is directly bonded to the aromatic ring contained in the specific cation [X] in that the effect of improving the sensitivity of the present composition is high. More preferably, two or more substituents ⁇ are directly attached to the aromatic ring.
• the specific cation structure [X] has one or two or more aromatic rings (hereinafter, also referred to as “aromatic ring Z”) bonded to a sulfonium cation or an iodonium cation, and has two or more substituents ⁇ .
• the specific cation structure [X] has one or more aromatic rings Z, and one or more of the aromatic rings Z has a structure in which two or more substituents ⁇ are bonded to the same aromatic ring.
• the aromatic ring Z examples include a benzene ring, a naphthalene ring, an anthracene ring and the like. Of these, the aromatic ring Z is preferably a benzene ring or a naphthalene ring, and is particularly preferably a benzene ring.
• the number of aromatic rings Z contained in the specific cation [X] is not particularly limited, but one or more is preferable, and two or more are more preferable. Regarding the total number of substituents ⁇ bonded to the aromatic ring Z in the specific cation structure [X], the description of the number of substituents ⁇ possessed by the specific cation structure [X] is applied.
• the total number of substituents ⁇ bonded to the aromatic ring Z is preferably 3 or more, and more preferably 4 or more. Further, from the viewpoint of balancing the effect of improving sensitivity and the ease of synthesis, the total number of substituents ⁇ bonded to the aromatic ring Z is preferably 10 or less, more preferably 8 or less, and further preferably 7 or less. Preferably, 6 or less are even more preferable.
• the specific cation structure [X] preferably has a triarylsulfonium cation structure or a diaryliodonium cation structure.
• the specific cation structure [X] is preferably a partial structure represented by the following formula (1) or a structure represented by the following formula (2).
• R 1a , R 2a and R 3a are independently fluoro or fluoroalkyl groups, respectively.
• R 4a and R 5a are independently monovalent substituents or are each.
• R 4a and R 5a represent a single bond or divalent group connecting the rings to which they are bonded together;
• R 6a is a monovalent substituent;
• a1 is an integer of 0-4.
• .A2 and a3 are independently integers of 0 to 5, where a1 + a2 + a3 ⁇ 2.
• a4, a5 and a6 are independently integers of 0 to 3.
• r is 0 or 1. However, a1 + a4 ⁇ 4, a2 + a5 ⁇ 5, and a3 + a6 ⁇ 2 ⁇ r + 5 are satisfied. “*” Indicates that the bond is a bond.
• R 7a and R 8a are independently fluorogroups or fluoroalkyl groups, respectively.
• R 9a and R 10a are independently monovalent substituents.
• a7 is an integer from 0 to 5.
• a8 is an integer from 0 to 4.
• a7 + a8 ⁇ 2 is satisfied.
• a9 and a10 are independently integers of 0 to 3. However, it satisfies a7 + a9 ⁇ 5 and a8 + a10 ⁇ 4. "*" Indicates that it is a bond. )
• the fluoroalkyl groups of R 1a , R 2a , R 3a , R 7a and R 8a may be linear or branched.
• the fluoroalkyl group preferably has 1 to 10 carbon atoms, and is, for example, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, 2,2,3,3,3-.
• Pentafluoropropyl group 1,1,1,3,3,3-hexafluoropropyl group, perfluoron-propyl group, perfluoroisopropyl group, perfluoron-butyl group, perfluoroisobutyl group, perfluorot- Examples thereof include a butyl group, a 2,2,3,3,4,5,5-octafluoropentyl group, a perfluorohexyl group and the like.
• the fluoroalkyl group of R 1a , R 2a , R 3a , R 7a and R 8a is preferably a group having 1 to 5 carbon atoms, and is preferably a trifluoromethyl group, a 2,2,2-trifluoroethyl group or a group. Perfluoroethyl groups are more preferred.
• R 1a , R 2a , R 3a , R 7a and R 8a are preferably a fluoro group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group or a perfluoroethyl group, preferably fluoro.
• a group or a trifluoromethyl group is more preferable, and a fluoro group is particularly preferable.
• an onium salt having a structure in which a fluoro group is directly bonded to the aromatic ring in the triarylsulfonium cation structure or the diaryliodonium cation structure the sensitivity of the present composition can be further improved, and the CDU performance and the development residue inhibitory property can be improved. It is preferable in that an excellent composition can be obtained.
• the monovalent substituent represented by R 4a , R 5a , R 6a , R 9a and R 10a is a group different from the substituent ⁇ .
• Specific examples of the monovalent substituent represented by R 4a , R 5a , R 6a , R 9a and R 10a include a chloro group, a bromo group, an iodo group, a substituted or unsubstituted alkyl group (however, fluoroalkyl).
• Excluding groups substituted or unsubstituted alkoxy group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted cycloalkyloxy group, ester group, alkylsulfonyl group, cycloalkylsulfonyl group, hydroxy group, carboxy group. , Cyano group, nitro group and the like.
• the alkyl groups represented by R 4a , R 5a , R 6a , R 9a and R 10a may be linear or branched.
• the alkyl group preferably has 1 to 10 carbon atoms, and is, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, or t.
• -Butyl group, n-pentyl group, neopentyl group and the like can be exemplified.
• the alkyl group of R 4a , R 5a , R 6a , R 9a and R 10a preferably has 1 to 5 carbon atoms, and a methyl group, an ethyl group, an n-butyl group or a t-butyl group is used. More preferred.
• the alkyl groups of R 4a , R 5a , R 6a , R 9a and R 10a have a substituent
• the substituent may be, for example, a chloro group, a bromo group, an iodine group, a hydroxy group, a carboxy group, a cyano group, etc. Examples thereof include a nitro group and an alkoxy group having 1 to 5 carbon atoms.
• R 4a , R 5a , R 6a , R 9a and R 10a are substituted or unsubstituted alkoxy groups
• the alkyl group portion constituting the alkoxy group is substituted or unsubstituted as exemplified above.
• Groups having an alkyl group can be mentioned.
• the alkoxy group is particularly preferably a methoxy group, an ethoxy group, an n-propoxy group or an n-butoxy group.
• the cycloalkyl group represented by R 4a , R 5a , R 6a , R 9a and R 10a may be monocyclic or polycyclic.
• examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like.
• Examples of the polycyclic cycloalkyl group include a norbornyl group, an adamantyl group, a tricyclodecyl group, a tetracyclododecyl group and the like.
• the substituent may be, for example, a chloro group, a bromo group, an iodine group, a hydroxy group, a carboxy group or a cyano group. , Nitro group, alkoxy group having 1 to 5 carbon atoms and the like.
• R 4a , R 5a , R 6a , R 9a and R 10a are substituted or unsubstituted cycloalkyloxy groups are exemplified above in the cycloalkyl group moiety constituting the cycloalkyloxy group.
• examples thereof include a group having a substituted or unsubstituted cycloalkyl group.
• the alkoxy group is particularly preferably a cyclopentyloxy group or a cyclohexyloxy group.
• R 4a , R 5a , R 6a , R 9a and R 10a are ester groups (-COOR), the hydrocarbon moiety (R) of the ester group is the substituted or unsubstituted alkyl group exemplified above. Alternatively, a substituted or unsubstituted cycloalkyl group can be mentioned. Of these, when R 4a , R 5a , R 6a , R 9a and R 10a are ester groups, they are preferably a methoxycarbonyl group, an ethoxycarbonyl group, or an n-butoxycarbonyl group.
• R 4a , R 5a , R 6a , R 9a and R 10a are alkylsulfonyl groups
• examples of the alkyl group moiety constituting the alkylsulfonium group include substituted or unsubstituted alkyl groups exemplified above.
• R 4a , R 5a , R 6a , R 9a and R 10a are cycloalkylsulfonyl groups
• the alkyl group moiety constituting the cycloalkylsulfonium group is the substituted or unsubstituted cycloalkyl group exemplified above. Can be mentioned.
• the divalent group may be, for example, -COO-, -OCO-, -CO-, -O. -, -SO-, -SO 2- , -S-, alkanediyl group with 1 to 3 carbon atoms, alkenyl group with 2 or 3 carbon atoms, -O-, -S- between carbon-carbon bonds of ethylene group , -COO-, -OCO-, -CO-, -SO-, or -SO 2 -groups and the like.
• R 4a and R 5a are single-bonded or divalent groups that combine the rings to which they are bonded together, then R 4a and R 5a are single-bonded, -O- or -S-. Is preferably formed.
• the total number of a1, a2 and a3 is 2 or more, more preferably 3 or more, further preferably 3 to 6, and even more preferably 4 to 6.
• the total number of a7 and a8 is 2 or more, and more preferably 2 to 6.
• the bond (*) in the above formulas (1) and (2) may be bonded to a hydrogen atom or a monovalent group (fluoro group, hydroxy group, alkyl group, etc.). good. Alternatively, it may be bonded to an atom constituting the main chain or side chain of the polymer.
• Specific examples of the specific cation structure [X] include a structure represented by the following formula and a structure in which one arbitrary hydrogen atom is removed from the benzene ring of the organic cation represented by the following formula.
• the structure of the specific cation structure [X] is not limited to the following structure.
• Specific anion structure [Y] examples include a sulfonate anion structure, an imide anion structure, a methyl anion structure, a carboxylate anion structure, and the like. Of these, the specific anion structure [Y] preferably has a sulfonate anion structure or a carboxylate anion structure.
• the number of iodine groups in the specific anion structure [Y] may be one or more.
• the number of iodine groups in the specific anion structure [Y] is preferably 2 or more, and 3 or more, in that the sensitivity can be increased while maintaining the CDU performance of the present composition and the dissolution contrast with respect to the developing solution. It is more preferable to have. From the viewpoint of balancing the effect of improving sensitivity and the ease of synthesis, the number of iodine groups of the specific anion structure [Y] is preferably 5 or less, and more preferably 4 or less.
• the bond position of the iodine group in the specific anion structure [Y] is not particularly limited.
• the iodine group of the specific anion structure [Y] is preferably directly bonded to the aromatic ring of the specific anion structure [Y] in that the effect of improving the sensitivity of the present composition is high.
• the specific anion structure [Y] has two or more iodine groups
• the two or more iodine groups may be bonded to the same aromatic ring in the specific anion structure [Y], and different aromatic rings. It may be bound to.
• the aromatic ring to which the iodine group is bonded is preferably a benzene ring and a naphthalene ring, and more preferably a benzene ring.
• the total number of iodine groups bonded to the aromatic ring in the specific anion structure [Y] is preferably 2 or more, and more preferably 3 or more. Further, from the viewpoint of balancing the effect of improving sensitivity and the ease of synthesis, the total number of iodine groups bonded to the aromatic ring is preferably 5 or less, and more preferably 4 or less.
• the specific anion structure [Y] preferably has a benzoyloxy group-containing sulfonium anion structure or a benzoyloxy group-containing carboxylate anion structure.
• the specific anion structure [Y] is preferably a sulfonium anion structure or a carboxylate anion structure having a partial structure represented by the following formula (3).
• R 11 is a monovalent substituent.
• L 1b is a single bond or a (c1 + 1) -valent organic group having 1 to 20 carbon atoms.
• B1 is an integer of 1 to 5.
• B2 is an integer of 0 to 4. However, b1 + b2 ⁇ 5 is satisfied.
• C1 is an integer of 1 to 3.
• "*" Indicates a bond.
• the monovalent substituent of R 11 is a group exemplified as a monovalent substituent of R 4a , R 5a , R 6a , R 9a and R 10a in the above formula (1).
• a monovalent hydrocarbon group having 1 to 20 carbon atoms and an arbitrary methylene group possessed by the hydrocarbon group are -O-, -S-, and -COO.
• -, -OCO-, -CO- or -NH- is replaced with a monovalent group having 1 to 20 carbon atoms, and any hydrogen atom of the hydrocarbon group is a fluoro group, a hydroxy group, a carboxy group, or a cyano group. Examples thereof include a monovalent group substituted with a group, a nitro group or an ester group.
• the "hydrocarbon group” in the present specification includes a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group.
• This "hydrocarbon group” may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
• the "chain hydrocarbon group” refers to a hydrocarbon group having only a chain structure without containing a cyclic structure, and includes both a linear hydrocarbon group and a branched hydrocarbon group.
• the "alicyclic hydrocarbon group” refers to a hydrocarbon group containing only an alicyclic structure as a ring structure and not containing an aromatic ring structure. Alicyclic hydrocarbon groups include both monocyclic alicyclic hydrocarbon groups and polycyclic alicyclic hydrocarbon groups.
• aromatic hydrocarbon group refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it does not have to be composed only of an aromatic ring structure, and a chain structure or an alicyclic structure may be contained in a part thereof.
• Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms include an alkyl group such as a methyl group, an ethyl group, an n-propyl group and an i-propyl group; and an alkenyl such as an ethenyl group, a propenyl group and a butenyl group.
• the monovalent chain hydrocarbon group having 1 to 20 carbon atoms represented by R 32 and R 33 is preferably an alkyl group or an alkenyl group, and an alkyl group or an alkenyl group having 1 to 4 carbon atoms. Groups are more preferred, and methyl, ethyl, i-propyl or t-butyl groups are even more preferred.
• Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a monovalent monovalent alicyclic saturated hydrocarbon group such as a cyclopentyl group and a cyclohexyl group; a cyclopentenyl group, a cyclohexenyl group and the like.
• Monovalent monocyclic alicyclic unsaturated hydrocarbon group monovalent polycyclic alicyclic saturated hydrocarbon group such as norbornyl group, adamantyl group, tricyclodecyl group, tetracyclododecane; Examples thereof include monovalent polycyclic alicyclic unsaturated hydrocarbon groups such as norbornenyl group and tricyclodecenyl group.
• the monovalent alicyclic chain hydrocarbon groups represented by R 32 and R 33 are monovalent monocyclic alicyclic saturated hydrocarbon groups and monovalent polycyclic alicyclic saturated. It is preferably a hydrocarbon group, more preferably a cyclopentyl group, a cyclohexyl group, a norbornyl group or an adamantyl group.
• Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include an aryl group such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, a naphthyl group, a methylnaphthyl group, an anthryl group and a methyl anthryl group; Examples thereof include an aralkyl group such as a benzyl group, a phenethyl group, a naphthylmethyl group and an anthrylmethyl group.
• the monovalent aromatic hydrocarbon group represented by R 32 and R 33 is preferably a phenyl group or a naphthyl group.
• a (c1 + 1) -valent hydrocarbon group having 1 to 20 carbon atoms and an arbitrary methylene group possessed by the hydrocarbon group are -O-, -S- or -NH-.
• the substituted (c1 + 1) valent group having 1 to 20 carbon atoms, or any hydrogen atom of the hydrocarbon group was substituted with a fluoro group, a hydroxy group, a carboxy group, a cyano group, a nitro group or an ester group ( c1 + 1) Group of valence and the like can be mentioned.
• Examples of the (c1 + 1) -valent hydrocarbon group having 1 to 20 carbon atoms represented by L 1b include a (c1 + 1) -valent linear or branched chain hydrocarbon group having 1 to 20 carbon atoms and carbon. Examples thereof include an alicyclic hydrocarbon group having a (c1 + 1) valence of several 3 to 20, an aromatic hydrocarbon group having a (c1 + 1) valence having 6 to 20 carbon atoms, and the like.
• L1b is a substituted or unsubstituted divalent chain hydrocarbon group in that the sensitivity of the present composition can be further improved, and the following formula (Lb-1) is preferable. ) Is particularly preferable.
• L 1b is preferably a substituted or unsubstituted trivalent or tetravalent chain hydrocarbon group, and R 31 in the group represented by the following formula (Lb-1). It is particularly preferable that the group is a trivalent or tetravalent group obtained by removing one or two hydrogen atoms from an alkanediyl group having 1 to 6 carbon atoms.
• R 61 is a single bond or an alkanediyl group having 1 to 6 carbon atoms.
• R 62 is an alkyl group having 1 to 6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon atoms. It is a group. "*" Indicates that it is a bond.
• the alkanediyl group having 1 to 6 carbon atoms represented by R 61 may be linear or branched.
• the alkanediyl group having 1 to 6 carbon atoms represented by R 61 is preferably 1 to 3 carbon atoms, and more preferably a methylene group or an ethylene group.
• the alkyl group having 1 to 6 carbon atoms represented by R 62 may be linear or branched.
• the alkyl group having 1 to 6 carbon atoms represented by R 62 is preferably 1 to 3 carbon atoms, and more preferably a methyl group, an ethyl group or an isopropyl group.
• the fluoroalkyl group having 1 to 6 carbon atoms represented by R 62 may be linear or branched.
• the fluoroalkyl group having 1 to 6 carbon atoms represented by R 62 is preferably 1 to 3 carbon atoms, and more preferably a perfluoromethyl group, a 2,2,2-trifluoroethyl group or a perfluoroethyl group. , And more preferably a perfluoromethyl group.
• b1 is preferably 2 or more, and more preferably 3 or more.
• b2 is preferably 0 to 2, more preferably 0.
• c1 is preferably 1 or 2, more preferably 1.
• the bond (*) in the above formula (3) may be bonded to a hydrogen atom or a monovalent group such as a fluoro group, a hydroxy group or an alkyl group.
• the bond (*) in the above formula (3) may be bonded to an atom constituting the main chain or side chain of the polymer.
• specific anion structure [Y] examples include a structure represented by the following formula, a partial structure in which one hydrogen atom is removed from the benzene ring of the organic cation represented by the following formula, and the like. ..
• the specific anion structure [Y] is not limited to the following structure.
• a preferred embodiment of the present composition is a polymer composition containing (A) a polymer and (B) an acid generator, and further, as suitable components, (C) an acid diffusion control agent and (D) a solvent. , And (E) one or more of the high fluorine-containing polymers may be contained.
• a component will be described in detail.
• the polymer is a polymer having a structural unit (I).
• the polymer (A) preferably constitutes the base resin of the present composition.
• base resin as used herein means a component that occupies 50% by mass or more with respect to the total amount of solid content contained in the present composition.
• the present composition may contain only one kind of the polymer (A), or may contain two or more kinds of the polymer.
• total amount of solid content is the sum of the components other than (D) the solvent.
• the ratio of the structural unit (I) in the (A) polymer is preferably 5 mol% or more, more preferably 10 mol% or more, based on the total structural units constituting the (A) polymer. It is preferably 20 mol% or more, and more preferably 20 mol% or more.
• the ratio of the structural unit (I) is preferably 80 mol% or less, more preferably 70 mol% or less, and 60 mol, based on all the monomers constituting the polymer (A). % Or less is more preferable.
• LWR Line Width Roughness
• the polymer may further have a structural unit (hereinafter, also referred to as “other structural unit”) different from the structural unit (I).
• other structural units include the following structural units (II) to (V).
• V Structural unit having an alcoholic hydroxyl group
• the polymer (A) further has a structural unit having an acid dissociative group (hereinafter, also referred to as “structural unit (II)”).
• the "acid dissociative group” as used herein refers to a group that replaces a hydrogen atom of an acid group such as a carboxy group or a hydroxy group and that dissociates due to the action of an acid.
• the acid dissociative group is dissociated by the acid generated by the exposure to generate a carboxy group, a hydroxy group, etc., and the polymer component is dissolved in the developing solution. The sex can be changed. This is preferable in that good lithography characteristics can be imparted to the present composition and a good resist pattern can be formed.
• the structural unit (II) is not particularly limited as long as it has an acid dissociative group, but is, for example, a structural unit represented by the following formula (ii-1) (hereinafter, “structural unit (II-1)””. Also referred to as), structural units represented by the following formula (ii-2) (hereinafter, also referred to as “structural unit (II-2)”) and the like.
• structural unit (II-1) hereinafter, “structural unit (II-1)””.
• structural units represented by the following formula (ii-2) hereinafter, also referred to as “structural unit (II-2)”
• R 12 is a hydrogen atom, a fluoro group, a methyl group or a trifluoromethyl group.
• R 13 is a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• R 15 are independently monovalent hydrocarbon groups having 1 to 20 carbon atoms, or carbon in which R 14 and R 15 are combined with each other and composed of carbon atoms to which R 14 and R 15 are bonded. It represents an alicyclic structure of the number 3 to 20.
• R 16 is a hydrogen atom or a methyl group.
• L 3 is a single bond, -COO- or -CONH-.
• R 17 , R 18 and R 19 are independently hydrogen atoms, monovalent hydrocarbon groups having 1 to 20 carbon atoms, or monovalent oxyhydrocarbon groups having 1 to 20 carbon atoms.
• R 12 is preferably a hydrogen atom or a methyl group, preferably a methyl group, from the viewpoint of copolymerizability of the monomer giving the structural unit (II-1). Is more preferable.
• R 16 is preferably a hydrogen atom from the viewpoint of copolymerizability of the monomer giving the structural unit (II-2).
• Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 13 to R 15 and R 17 to R 19 include a monovalent chain hydrocarbon group having 1 to 20 carbon atoms and 3 carbon atoms. Examples thereof include a monovalent alicyclic hydrocarbon group having about 20 to 20 and a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Specific examples of these include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl group as monovalent chain hydrocarbon groups having 1 to 20 carbon atoms.
• Alkyl groups such as sec-butyl group, t-butyl group and pentyl group; alkenyl groups such as ethenyl group, propenyl group, butenyl group and pentenyl group; alkynyl groups such as ethynyl group, propynyl group, butynyl group and pentynyl group Can be mentioned.
• the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms includes a monocyclic alicyclic saturated hydrocarbon group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; a norbornyl group, an adamantyl group, and a tri.
• Polycyclic alicyclic saturated hydrocarbon groups such as cyclodecyl group and tetracyclododecyl group; monocyclic alicyclic unsaturated hydrocarbon groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group and cyclohexenyl group; norbornenyl.
• Examples thereof include a polycyclic alicyclic saturated hydrocarbon group such as a group and a tricyclodecenyl group.
• Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group and an anthryl group; a benzyl group, a phenethyl group, a naphthylmethyl group and an anthrylmethyl group.
• An aralkyl group such as, etc. can be mentioned.
• the alicyclic structure having 3 to 20 carbon atoms in which R 14 and R 15 are combined with each other and together with the carbon atom to which R 14 and R 15 are bonded includes a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, and a cyclo.
• Monocyclic alicyclic structures such as heptane structure and cyclooctane structure; polycyclic alicyclic structures such as norbornan structure, adamantan structure, tricyclodecane structure and tetracyclododecane structure can be mentioned.
• Examples of the monovalent oxyhydrocarbon group having 1 to 20 carbon atoms represented by R 17 , R 18 and R 19 include 1 of the carbon atoms 1 to 20 of the above R 13 to R 15 and R 17 to R 19 .
• Examples of the valent hydrocarbon group include those containing an oxygen atom at the end on the bond hand side.
• R 17 , R 18 and R 19 are preferably a chain hydrocarbon group or a cycloalkyloxy group.
• structural unit (II-1) examples include structural units represented by the following equations.
• RA1 is a hydrogen atom, a fluoro group, a methyl group or a trifluoromethyl group.
• structural unit (II-2) include structural units represented by the following equations. (In the formula, R 16 is a hydrogen atom or a methyl group.)
• the content ratio of the structural unit (II) is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 35 mol% or more, based on all the structural units constituting the polymer (A).
• the content ratio of the structural unit (II) is preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 65 mol% or less, based on all the structural units constituting the polymer (A).
• the present composition may contain a polymer having a structural unit (II) in addition to the polymer having the structural unit (I) (that is, the polymer (A)).
• a polymer having a structural unit (I) and no structural unit (II) include, for example, a polymer having a structural unit (I) and no structural unit (II), and a polymer having a structural unit (II) and having a structural unit (I).
• Aspects containing a polymer that does not have a structure; a polymer having a structural unit (I) and a structural unit (II) and a polymer having a structural unit (II) and not having a structural unit (I), etc. Can be mentioned.
• this composition has a structural unit (I) and a structural unit (II) as the (A) polymer. It preferably contains at least a polymer.
• the structural unit (III) is typically a structural unit derived from an onium salt having a group involved in polymerization (preferably a polymerizable carbon-carbon unsaturated bond-containing group). Having the structural unit (III) in the polymer (A) is preferable in that the effect of reducing the development residue can be further enhanced.
• the structural unit (III) can be expressed as a structural unit derived from the monomer represented by the following formula (3A) or formula (3B).
• formula (3A) L 7 is a group involved in the polymerization. “L 7 ⁇ Z + ” is a radiation-sensitive onium cation. “M ⁇ ” is an organic anion.
• Formula (3B). ) L 7 is a group involved in polymerization. "Z + " is a radiation-sensitive onium cation.
• L 7 - M- is an organic anion.
• the group represented by L 7 is preferably a group containing a polymerizable carbon-carbon unsaturated bond.
• Specific examples thereof include a vinyl group, a vinyl ether group, a vinylphenyl group, a (meth) acryloyl group, a maleimide group and the like.
• the structural unit (III) is preferably a structural unit derived from the monomer represented by the above formula (3B) in terms of ease of synthesizing the polymer.
• the radiation-sensitive onium cation contained in the monomer constituting the structural unit (III) may have a specific cation structure [X] and does not have a specific cation structure [X], that is, is substituted. It may have only one group ⁇ or no substituent ⁇ . Further, the organic anion contained in the monomer constituting the structural unit (III) may have a specific anion structure [Y] or may not have an iodine group. Examples of the monomer constituting the structural unit (III) include the following monomers [A1] to [A4].
• a monomer consisting of a radiation-sensitive onium cation having two or more substituents ⁇ and an organic anion having an iodo group, and containing a group in which either the radiation-sensitive onium cation or the organic anion is involved in polymerization. .. [A2] It consists of a radiation-sensitive onium cation having only one substituent ⁇ or no substituent ⁇ , and an organic anion having an iodo group, and either the radiation-sensitive onium cation or the organic anion is polymerized. A monomer containing a group involved.
• [A3] It consists of a radiation-sensitive onium cation having two or more substituents ⁇ and an organic anion structure having no iodo group, and contains a group in which either the radiation-sensitive onium cation or the organic anion is involved in the polymerization.
• Quantitative body. It consists of a radiation-sensitive onium cation having only one substituent ⁇ or no substituent ⁇ , and an organic anion structure having no iodo group, and either a radiation-sensitive onium cation or an organic anion is used.
• Preferred examples of the structural unit (III) are a structural unit represented by the following formula (iii-1), a structural unit represented by the following formula (iii-2), and a structural unit represented by the following formula (iii-3).
• Structural units can be mentioned.
• R 20 is a hydrogen atom or a methyl group.
• L 4 is a single bond, -O- or -COO-.
• R 23 is a substitution or substitution of 1 to 6 carbon atoms.
• R 21 and R 22 are independent of each other.
• M ⁇ is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. It is an organic anion.
• R20 is a hydrogen atom or a methyl group.
• L 5 is a single bond, -R 30a -CO-O-, -R 30a -O- or -R 30a -O-CO-.
• R 30a is a divalent group containing -O-, -CO- or -COO- between carbon-carbon bonds of an alkanediyl group having 1 to 12 carbon atoms or an alkanediyl group having 2 to 12 carbon atoms.
• R 24 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluoroalkyl group having 1 to 10 carbon atoms.
• Y + is a radiation-sensitive onium cation represented by the following formula (Y-1) or formula (Y-2).
• R20 is a hydrogen atom or a methyl group.
• L 6 is a single bond, a substituted or unsubstituted alkanediyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, a substituted or unsubstituted arylene group having 6 to 12 carbon atoms, and the like.
• -CO-OR 30b -or-CO-NH-R 30b- .
• R 30b contains -O-, -CO- or -COO- between carbon-carbon bonds of a substituted or unsubstituted alkanediyl group having 1 to 6 carbon atoms or an alkanediyl group having 2 to 6 carbon atoms. It is the basis of the price.
• Y + is a radiation-sensitive onium cation represented by the following formula (Y-1) or formula (Y-2).
• R 25 to R 29 are independently substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, and substituted or absent with 2 to 12 carbon atoms, respectively. It is a substituted alkenyl group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
• the respective groups of R 21 to R 23 and R 25 to R 29 are substituted.
• the substituent may be, for example, a fluoro group, a chloro group, a bromo group, an iodine group, an alkoxy group, a cycloalkyloxy group, or an ester group.
• the organic cation in the monomer constituting the structural unit represented by the above formula (iii-1) and the organic cation represented by the above formula (Y-1) have a triarylsulfonium cation structure. Is preferable.
• the organic cations in the above formulas (iii-2) and (iii-3) preferably have a triarylsulfonium cation structure or a diaryliodonium cation structure.
• the organic cation represented by the above formula (Y-2) preferably has a diaryliodonium cation structure.
• specific examples of the specific cation [X] include the structures exemplified above.
• the structural unit (III) for example, as a structural unit having a partial structure represented by the above formula (3B), it is represented by each of the following formulas (iii-1a) to (iii-7a). Structural units and the like can be mentioned.
• Examples of the structural unit having a partial structure represented by the above formula (3A) include structural units represented by the following formulas (iii-8a) and (iii-9a).
• R20 is a hydrogen atom or a methyl group.
• Y + is represented by the above formula (Y-1) or formula (Y-2). Radiation sensitive onium cation.
• M - is an organic anion.
• the content ratio of the structural unit (III) is preferably 20 mol% or more, preferably 30 mol%, based on the total structural units constituting the polymer (A). The above is more preferable, and 35 mol% or more is further preferable.
• the content ratio of the structural unit (III) is preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 65 mol% or less, based on all the structural units constituting the polymer (A).
• the structural unit (IV) corresponds to a structural unit having a lactone structure, a cyclic carbonate structure, a sultone structure, or a ring structure in which two or more of these are combined (however, structural units (I) to (III)). Except for).
• the polymer further contains the structural unit (IV), so that the solubility in a developing solution can be adjusted, and as a result, the lithography characteristics of the present composition can be further improved. Further, when the polymer (A) further contains the structural unit (IV), the adhesion between the resist film obtained by using the present composition and the substrate can be improved.
• Examples of the structural unit (IV) include structural units represented by the following formulas.
• RL1 is a hydrogen atom, a fluoro group, a methyl group or a trifluoromethyl group.
• the content ratio of the structural unit (IV) is preferably 5 mol% or more, preferably 10 mol%, based on all the structural units constituting the polymer (A).
• the above is more preferable, and 15 mol% or more is further preferable.
• the content ratio of the structural unit (IV) is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, based on all the structural units constituting the polymer (A).
• the structural unit (V) is a structural unit having an alcoholic hydroxyl group (however, excluding those corresponding to the structural units (I) to (IV)).
• the "alcoholic hydroxyl group” in the present specification is a group having a structure in which a hydroxyl group is directly bonded to an aliphatic hydrocarbon group.
• the aliphatic hydrocarbon group may be a chain hydrocarbon group or an alicyclic hydrocarbon group.
• the polymer has a structural unit (V) further, so that the solubility in a developing solution can be improved, and as a result, the lithography characteristics of the present composition can be further improved.
• the structural unit (V) is preferably a structural unit derived from an unsaturated monomer having an alcoholic hydroxyl group.
• the unsaturated monomer is not particularly limited, and examples thereof include 3-hydroxyadamantane-1-yl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
• the content ratio of the structural unit (V) is preferably 1 mol% or more, preferably 3 mol%, based on all the structural units constituting the polymer (A). The above is more preferable.
• the content ratio of the structural unit (V) is preferably 30 mol% or less, more preferably 10 mol% or less, based on all the structural units constituting the polymer (A).
• Other structural units include, for example, structural units containing a cyano group, a nitro group or a sulfonamide group (for example, a structural unit derived from 2-cyanomethyladamantan-2-yl (meth) acrylate).
• Structural unit containing a halogen atom eg, structural unit derived from 2,2,2-trifluoroethyl (meth) acrylate, 1,1,1,3,3,3-hexafluoropropane-2-yl (meth) Structural units derived from acrylate, structural units derived from 4-iodostyrene, etc.
• structural units containing non-acid dissociable hydrocarbon groups eg, structural units derived from styrene, structural units derived from vinylnaphthalene, n -Structural units derived from pentyl (meth) acrylate, etc.
• the content ratio of these structural units can be appropriately set according to each structural unit as long as the effects of the present disclosure are not impaired.
• the content ratio of the polymer (A) in the present composition is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, based on the total amount of the solid content contained in the present composition. ..
• the content ratio of the polymer (A) is preferably 99% by mass or less, more preferably 98% by mass or less, still more preferably 95% by mass or less, based on the total amount of the solid content contained in the present composition.
• the polymer (A) can be synthesized, for example, by polymerizing a monomer giving each structural unit in an appropriate solvent using a radical polymerization initiator or the like.
• radical polymerization initiator examples include azobisisobutyronitrile (AIBN), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), and 2,2'-azobis (2-cyclopropyl). Propionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate and other azo radical initiators; benzoyl peroxide, t-butyl hydroperoxide , Peroxide radical initiators such as cumenehydroperoxide and the like. Of these, AIBN and dimethyl 2,2'-azobisisobutyrate are preferable, and AIBN is more preferable. As the radical polymerization initiator, one kind may be used alone or two or more kinds may be mixed and used.
• 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, norbornan.
• Cycloalkanes such as; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutanes, bromohexanes, dichloroethanes, hexamethylenedibromid, halogenated hydrocarbons such as chlorobenzene; ethyl acetate, etc.
• Saturated carboxylic acid esters such as n-butyl acetate, i-butyl acetate, methyl propionate; ketones such as acetone, butanone, 4-methyl-2-pentanone, 2-heptanone; tetrahydrofuran, dimethoxyethane, diethoxyethane
• ketones such as acetone, butanone, 4-methyl-2-pentanone, 2-heptanone
• tetrahydrofuran dimethoxyethane, diethoxyethane
• ethers examples of ethers
• alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 4-methyl-2-pentanol and the like can be mentioned.
• the solvent used for these polymerizations one kind may be used alone or two or more kinds may be mixed and used.
• the reaction temperature in the polymerization is preferably 40 ° C. or higher, more preferably 50 ° C. or higher.
• the reaction temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower.
• the reaction time in the polymerization is preferably 1 hour or more, more preferably 2 hours or more.
• the reaction time is preferably 48 hours or less, more preferably 24 hours or less.
• the polystyrene-equivalent weight average molecular weight (Mw) of the polymer by gel permeation chromatography (GPC) is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 3,000 or more, and 5 000 or more is particularly preferable.
• the Mw is preferably 50,000 or less, more preferably 30,000 or less, still more preferably 20,000 or less, and particularly preferably 10,000 or less.
• GPC gel permeation chromatography
• the ratio (Mw / Mn) of Mw to the polystyrene-equivalent number average molecular weight (Mn) of the polymer by GPC is preferably 5.0 or less, more preferably 3.0 or less, still more preferably 2.0 or less. Further, Mw / Mn is usually 1 or more, preferably 1.3 or more.
• the acid generator is typically a substance containing a radiation sensitive onium cation and an organic anion.
• the acid generator (B) may be a small molecule compound or a polymer (however, excluding the polymer (A)).
• the (B) acid generator is a small molecule compound
• [LB3] An onium salt composed of a radiation-sensitive onium cation having two or more substituents ⁇ and an organic anion having no iodine group.
• the radiation-sensitive onium cations having two or more substituents ⁇ include the radiation-sensitive onium cation having a partial structure represented by the above formula (1) and the above-mentioned formula (1).
• Examples thereof include radiation-sensitive onium cations having a partial structure represented by 2).
• Examples of the organic anion having an iodine group include an organic anion having a partial structure represented by the above formula (3).
• Radiation-sensitive onium cations having only one substituent ⁇ or no substituent ⁇ The radiation-sensitive onium cations of the onium salts [LB2] and [LB4] do not have or have no substituent ⁇ . Any radiation-sensitive onium cation having only one ⁇ may be used, and its structure is not particularly limited. From the viewpoint of improving the lithography characteristics of the present composition, the radiation-sensitive onium cations of the onium salts [LB2] and [LB4] preferably have a sulfonium cation structure or an iodonium cation structure. Specific examples thereof include an organic cation represented by the following formula (4), an organic cation represented by the following formula (5), and an organic cation represented by the following formula (6).
• R 31 and R 32 are independently monovalent organic groups having 1 to 20 carbon atoms.
• K1 is an integer of 0 to 5.
• R is Reference numeral 33 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen group.
• the plurality of R33s are the same or different, and are monovalents having 1 to 20 carbon atoms.
• T1 is 0 or 1.
• the number of the substituent ⁇ is 0 or 1.
• k2 is an integer from 0 to 7.
• R 34 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen group.
• the plurality of R 34s are the same or different, and are monovalent organic groups, hydroxy groups, nitro groups or halogen groups having 1 to 20 carbon atoms, or 2 of the plurality of R 34s .
• k3 is an integer of 0 to 6.
• R35 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen group.
• the plurality of R 35s are the same or different, and are monovalent organic groups, hydroxy groups, nitro groups or halogen groups having 1 to 20 carbon atoms, or 2 of the plurality of R 35s .
• t3 is an integer of 0 to 3.
• R 36 is a single bond or a divalent organic group having 1 to 20 carbon atoms.
• t2 is 0 or 1.
• the number of the substituent ⁇ is 0 or 1.
• k4 is an integer of 0 to 5.
• R 37 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen group.
• the plurality of R 37s are the same or different, and are monovalent organic groups, hydroxy groups, nitro groups or halogen groups having 1 to 20 carbon atoms, or 2 of the plurality of R 37s . It represents a part of a ring structure having 4 to 20 ring members, in which one or more of them are combined with each other and formed together with a carbon chain to which they are bonded.
• k5 is an integer from 0 to 5.
• R 38 is a monovalent organic group having 1 to 20 carbon atoms, a hydroxy group, a nitro group or a halogen group.
• the plurality of R 38s are the same or different and are monovalent organic groups, hydroxy groups, nitro groups or halogen groups having 1 to 20 carbon atoms, or 2 of the plurality of R 38s . It represents a part of a ring structure having 4 to 20 ring members, in which one or more are combined with each other and formed together with a carbon chain to which they are bonded. However, in the formula (6), the number of the substituent ⁇ is 0 or 1. )
• the monovalent organic group having 1 to 20 carbon atoms represented by R 31 , R 32 and R 33 is replaced with a monovalent hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom.
• a hydrocarbon group having 1 to 20 carbon atoms substituted with a group is preferable, and a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a monovalent group having 6 to 20 carbon atoms in which a hydrogen atom is substituted with a substituent is preferable.
• the aromatic hydrocarbon group of is more preferable, and a substituted or unsubstituted phenyl group is further preferable.
• Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 31 , R 32 and R 33 include R 13 to R in the above formulas (ii-1) and (ii-2). Examples thereof include groups similar to those exemplified as the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by 15 and R 17 to R 19 .
• R 31 , R 32 and R 33 are represented by R 4a , R 5a , R 6a , R 9a and R 10a in the above formulas (1) and (2).
• Examples of the valence substituent include groups similar to those exemplified.
• k1 is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
• the value of t1 is preferably 0.
• R 34 and R 35 are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, ⁇ OR k , —COOR k , —O—CO—R k , ⁇ .
• OR kk -COOR k or -R kk -CO-R k is preferable.
• Rk is a monovalent hydrocarbon group having 1 to 10 carbon atoms.
• Rkk is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 34 and R 35 include R 13 to R 15 and R 17 to those in the above formulas (ii-1) and (ii-2).
• Examples thereof include the same groups as those exemplified as the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R19 . Further, in R 34 and R 35 , as the substituent for substituting the hydrogen atom of the hydrocarbon group, the same group as the group exemplified as the substituent of the groups represented by the above R 31 , R 32 and R 33 is used. Can be mentioned.
• Examples of the divalent organic group represented by R 36 include a group obtained by removing one hydrogen atom from a monovalent organic group having 1 to 20 carbon atoms exemplified as R 34 and R 35 .
• k3 is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. 0 is preferable for t2.
• t3 is preferably 2 or 3, more preferably 2.
• R 37 and R 38 are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, -OSO 2 -R k , -SO 2 -R k , -OR k . , -COOR k , -O-CO-R k , -OR kk -COOR k , -R kk -CO-R k or -SR k , or two or more of these groups are combined with each other.
• a ring structure composed is preferable.
• R k and R kk are synonymous with R kk and R kk contained in the group represented by the above-mentioned R 34 and R 35 .
• Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 37 and R 38 include R 13 to R 15 and R 17 to those in the above formulas (ii-1) and (ii-2). Examples thereof include the same groups as those exemplified as the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R19 .
• the substituent for substituting the hydrogen atom of the hydrocarbon group is the same group as the group exemplified as the substituent of the groups represented by R 31 , R 32 and R 33 .
• k4 and k5 an integer of 0 to 2 is preferable, 0 or 1 is more preferable, and 0 is further preferable.
• the radiation-sensitive onium cations contained in the onium salts [LB2] and [LB4] are the radiation-sensitive onium cation represented by the above formula (4) and the radiation-sensitive onium represented by the above formula (6). Cations are preferable, and radiation-sensitive onium cations having a triarylsulfonium cation structure or a diaryliodonium cation structure are more preferable.
• the radiation-sensitive onium cations of the onium salts [LB2] and [LB4] are the radiation-sensitive onium cation satisfying a1 + a2 + a3 ⁇ 1 in the above formula (1) and a7 + a8 ⁇ 1 in the above formula (2). From the viewpoint of improving the lithography characteristics of the present composition, the radiation-sensitive onium cation satisfying the above conditions (however, "*" in the formulas (1) and (2) represents a bond with a hydrogen atom). Is particularly preferable.
• the organic anion of the onium salts [LB3] and [LB4] is not particularly limited as long as it is an organic anion having no iodine group.
• Examples of the organic anion contained in the onium salts [LB3] and [LB4] include an organic anion having a sulfonate anion structure, an imide anion structure, or a methide anion structure.
• the organic anion having the onium salt [LB3] and [LB4] is preferably an organic anion having a sulfonate anion structure.
• the organic anion represented by the following formula (7) can be preferably used as the organic anion contained in the onium salts [LB3] and [LB4].
• n1 is an integer of 0 to 10.
• n2 is an integer of 0 to 10.
• n3 is an integer of 1 to 10.
• n1 + n2 + n3 is 1 or more and 30 or less.
• the plurality of R p2s are the same group or different groups.
• R p3s are the same group or different groups, and the plurality of R p4s are the same group. Or different groups.
• n3 is 2 or more, the plurality of R p5s are the same group or different groups, and the plurality of R p6s are the same group or different groups.
• R p1 has 5 or more ring members. It is a monovalent group containing a ring structure.
• R p2 is a divalent linking group. However, R p1 and R p2 do not have an iodo group.
• R p3 and R p4 are independently hydrogen.
• R p5 and R p6 are independently hydrogen atoms, respectively. It is a fluoro group or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms. However, when n3 is 1, both R p5 and R p6 are not hydrogen atoms, and when n3 is 2 or more, Multiple R p5 and R p6 are not all hydrogen atoms.
• the monovalent group containing a ring structure having 5 or more ring members represented by R p1 is, for example, a monovalent group containing an alicyclic structure having 5 or more ring members and 5 or more ring members.
• examples thereof include a monovalent group containing an aliphatic heterocyclic structure, a monovalent group containing an aromatic ring structure having 5 or more ring members, and a monovalent group containing an aromatic heterocyclic structure having 5 or more ring members.
• Examples of the alicyclic structure having 5 or more ring members include a monocyclic cycloalkane structure such as a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, a cyclooctane structure, a cyclononane structure, a cyclodecane structure, and a cyclododecane structure; a cyclopentene structure and a cyclohexene.
• a monocyclic cycloalkane structure such as a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, a cyclooctane structure, a cyclononane structure, a cyclodecane structure, and a cyclododecane structure
• a cyclopentene structure and a cyclohexene such as a cyclopentane structure, a cycl
• Monocyclic cycloalkene structure such as structure, cycloheptene structure, cyclooctene structure, cyclodecene structure; polycyclic cycloalkane structure such as norbornan structure, adamantan structure, tricyclodecane structure, tetracyclododecane structure; norbornene structure, tricyclodecene structure
• Examples thereof include a polycyclic cycloalkane structure such as a structure.
• Examples of the aliphatic heterocyclic structure having 5 or more ring members include a lactone structure such as a hexanolactone structure and a norbornane lactone structure; a sulton structure such as a hexanoslton structure and a norbornane sulton structure; an oxacycloheptane structure and an oxanorbornane structure.
• Examples thereof include an oxygen atom-containing heterocyclic structure such as a cyclic acetal structure; a nitrogen atom-containing heterocyclic structure such as an azacyclohexane structure and a diazabicyclooctane structure; a thiacyclohexane structure and a sulfur atom-containing heterocyclic structure having a thianorbornane structure.
• Examples of the aromatic ring structure having 5 or more ring members include a benzene structure, a naphthalene structure, a phenanthrene structure, an anthracene structure and the like.
• Examples of the aromatic heterocyclic structure having 5 or more ring members include an oxygen atom-containing heterocyclic structure such as a furan structure, a pyran structure, and a benzopyran structure; and a nitrogen atom-containing heterocyclic structure such as a pyridine structure, a pyrimidine structure, and an indole structure. Can be mentioned.
• a part or all of the hydrogen atom of the ring structure of R p1 may be substituted with a substituent.
• substituents include a fluoro group, a chloro group, a bromo group, a hydroxy group, a carboxy group, a cyano group, a nitro group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, an acyl group, an acyloxy group and the like.
• the monovalent group represented by R p1 is preferably a group having an aromatic ring structure having 5 or more ring members, and particularly preferably a group having a benzene structure.
• Examples of the divalent linking group represented by R p2 include a carbonyl group, an ether group, a carbonyloxy group, a sulfide group, a thiocarbonyl group, a sulfonyl group, and a divalent hydrocarbon group.
• a carbonyloxy group, a sulfonyl group, an alkanediyl group or a cycloalkandyl group is preferable, a carbonyloxy group or a cycloalkandyl group is more preferable, a carbonyloxy group or a norbornandyl group is further preferable, and a carbonyloxy group is preferable.
• a carbonyloxy group is preferable.
• Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R p3 and R p4 include an alkyl group having 1 to 20 carbon atoms.
• Examples of the monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms represented by R p3 and R p4 include a fluorinated alkyl group having 1 to 20 carbon atoms.
• a hydrogen atom, a fluoro group or a fluoroalkyl group is preferable, a fluoro group or a perfluoroalkyl group is more preferable, and a fluoro group or a trifluoromethyl group is further preferable.
• Examples of the monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms represented by R p5 and R p6 include a fluoroalkyl group having 1 to 20 carbon atoms.
• a fluoro group or a fluoroalkyl group is preferable, a fluoro group or a perfluoroalkyl group is more preferable, a fluoro group or a trifluoromethyl group is further preferable, and a fluoro group is particularly preferable.
• n3 1, it is preferable that both R p5 and R p6 are fluorogroups, or R p5 is a fluorogroup and R p6 is a trifluoromethyl group.
• N1 is preferably 0 to 5, more preferably 0 to 3, further preferably 0 to 2, and particularly preferably 0 or 1.
• n2 is preferably 0 to 5, more preferably 0 to 2, further preferably 0 or 1, and particularly preferably 0.
• n3 is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.
• the n1 + n2 + n3 is preferably 2 or more. Further, n1 + n2 + n3 is preferably 10 or less, more preferably 5 or less.
• the organic anions of the onium salts [LB3] and [LB4] preferably have a benzoyloxy group-containing sulfonium anion structure.
• "R p1- (R p2 ) n1- " in the above formula (7) preferably has a structure represented by the following formula (7A).
• the substituent represented by R p1 in the above formula (7) may have. Examples include the same groups as the examples.
• R p7 is a monovalent substituent.
• N4 is an integer of 0 to 5. “*” Indicates a bond.
• the onium salt [LB1] include, for example, a radiation-sensitive onium cation having a partial structure represented by the above formula (1) and an organic anion having a partial structure represented by the above formula (3).
• examples thereof include a compound composed of a radiation-sensitive onium cation having a partial structure represented by the above formula (2) and an organic anion having a partial structure represented by the above formula (3).
• the onium salt [LB2] a compound composed of a radiation-sensitive onium cation represented by the above formula (4) and an organic anion having a partial structure represented by the above formula (3), the above formula ( A compound composed of a radiation-sensitive onium cation represented by 5) and an organic anion having a partial structure represented by the above formula (3), a radiation-sensitive onium cation represented by the above formula (6), and the above.
• Examples thereof include a compound composed of an organic anion having a partial structure represented by the formula (3).
• onium salt [LB3] a compound composed of a radiation-sensitive onium cation having a partial structure represented by the above formula (1) and an organic anion represented by the above formula (7), the above formula ( Examples thereof include a compound composed of a radiation-sensitive onium cation having a partial structure represented by 2) and an organic anion represented by the above formula (7).
• the onium salt [LB4] include a compound composed of a radiation-sensitive onium cation represented by the above formula (4) and an organic anion represented by the above formula (7), and represented by the above formula (5).
• Examples thereof include compounds composed of organic anions.
• the molecular weight of the (B) acid generator is preferably 1000 or less, more preferably 900 or less, still more preferably 800 or less. It is even more preferably 600 or less. Further, when the (B) acid generator is a small molecule compound, the molecular weight of the (B) acid generator is, for example, 100 or more, more preferably 150 or more.
• the polymer (hereinafter, also referred to as “polymer (PB)”) is a polymer having the structural unit (III).
• the polymer (PB) is distinguished from the polymer (A) in that it does not have the structural unit (I).
• Specific examples of the polymer (PB) include the following polymers [PB1] to [PB4].
• [PB1] A monomer consisting of a radiation-sensitive onium cation having two or more substituents ⁇ and an organic anion having an iodo group, and containing a group in which either the radiation-sensitive onium cation or the organic anion is involved in polymerization.
• PB2 It consists of a radiation-sensitive onium cation having only one substituent ⁇ or no substituent ⁇ , and an organic anion having an iodo group, and either the radiation-sensitive onium cation or the organic anion is polymerized.
• PB3 It consists of a radiation-sensitive onium cation having two or more substituents ⁇ and an organic anion structure having no iodine group, and contains a group in which either the radiation-sensitive onium cation or the organic anion is involved in the polymerization.
• PB4 It consists of a radiation-sensitive onium cation having only one substituent ⁇ or no substituent ⁇ , and an organic anion structure having no iodo group, and either a radiation-sensitive onium cation or an organic anion is used.
• structural unit (III) contained in the polymer (PB) include structural units represented by the above formulas (iii-1a) to (iii-9a).
• the polymer (PB) may further have a structural unit different from the structural unit (III).
• Examples of the structural unit include structural units exemplified as other structural units in the description of (A) polymer.
• the polymer (PB) can be synthesized by the same method as described above as the method for synthesizing the polymer (A).
• the polystyrene-equivalent weight average molecular weight (Mw) by GPC is preferably 1,000 or more, more preferably 2,000 or more, further preferably 3,000 or more, and particularly preferably 5,000 or more. ..
• the Mw of the polymer (PB) is preferably 50,000 or less, more preferably 30,000 or less, still more preferably 20,000 or less, and particularly preferably 10,000 or less.
• the ratio (Mw / Mn) of Mw to the polystyrene-equivalent number average molecular weight (Mn) of the polymer (PB) by GPC is preferably 5 or less, more preferably 3 or less, still more preferably 2 or less, and 1.7. The following are particularly preferred.
• the Mw / Mn of the polymer (PB) is usually 1 or more, preferably 1.3 or more.
• low molecular weight compounds that is, onium salts [LB1] to [LB4]
• onium salt [LB1] and onium salt [LB2] are preferable.
• the content ratio of the (B) acid generator in the present composition is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, based on 100 parts by mass of the (A) polymer.
• the content ratio of the (B) acid generator is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, based on 100 parts by mass of the polymer (A).
• B) By setting the content ratio of the acid generator in the above range, it is preferable in that the defect suppressing property, the LWR performance and the sensitivity of the present composition can be further improved.
• As the acid generator one type may be used alone, or two or more types may be used in combination.
• the purpose of the acid diffusion control agent (C) is to suppress the chemical reaction due to the acid in the non-exposed region by suppressing the diffusion of the acid generated from the (B) acid generator in the resist film by exposure. Incorporated into the composition. (C) By blending the acid diffusion control agent into the present composition, it is preferable in that the lithography characteristics of the present composition can be further improved. Further, it is possible to suppress the change in the line width of the resist pattern due to the fluctuation of the leaving time from the exposure to the development process, and it is possible to obtain a radiation-sensitive composition having excellent process stability.
• Examples of the (C) acid diffusion control agent include nitrogen-containing compounds and photodisintegrating bases.
• a compound that generates a weaker acid than the acid generated by the (B) acid generator by exposure can be used.
• a weak acid preferably a carboxylic acid
• a sulfonic acid or a sulfonamide is generated by exposure.
• the magnitude of acidity can be evaluated by the acid dissociation constant (pKa).
• the acid dissociation constant of the acid at which the photodisintegrating base is generated is usually -3 or more, preferably -1 ⁇ pKa ⁇ 7, and more preferably 0 ⁇ pKa ⁇ 5.
• the acid diffusion control agent (C) is preferably a small molecule compound.
• the present composition contains (B) an acid generator and (C) an acid diffusion control agent
• the (C) acid diffusion control agent contains a photodisintegrant base
• the (B) acid generator is " It corresponds to the "first acid generator”
• the (C) acid diffusion control agent corresponds to the "second acid generator”.
• nitrogen-containing compound examples include a compound represented by the following formula (8) (hereinafter, also referred to as “nitrogen-containing compound (8A)”) and a compound having two nitrogen atoms (hereinafter, “nitrogen-containing compound”).
• Compound (8B) a compound having three nitrogen atoms (hereinafter, also referred to as“ nitrogen-containing compound (8C) ”), an amide group-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, and an acid dissociative group. Examples thereof include nitrogen-containing compounds having.
• R 41 , R 42 and R 43 are independently hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted aryl groups, or Substituted or unsubstituted aralkyl group.
• examples of the nitrogen-containing compound (8A) include monoalkylamines such as n-hexylamine; dialkylamines such as di-n-butylamine; triethylamine, tri-n-pentylamine and the like. Trialkylamines; examples include aromatic amines such as aniline and 2,6-diisopropylaniline.
• examples of the nitrogen-containing compound (8B) include ethylenediamine, N, N, N', N'-tetramethylethylenediamine and the like.
• examples of the nitrogen-containing compound (8C) include polyamine compounds such as polyethyleneimine and polyallylamine; and polymers such as dimethylaminoethylacrylamide.
• Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like.
• Examples of the urea compound include urea, methyl urea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tributylthiourea and the like. ..
• nitrogen-containing heterocyclic compound examples include pyridines such as pyridine and 2-methylpyridine; morpholines such as N-propylmorpholin and N- (undecane-1-ylcarbonyloxyethyl) morpholine; pyrazine and pyrazole and the like. Be done.
• nitrogen-containing compound having an acid-dissociating group examples include Nt-butoxycarbonylpiperidin, Nt-butoxycarbonylimidazole, Nt-butoxycarbonylbenzimidazole, and Nt-butoxycarbonyl-2-phenylbenz.
• Imidazole N- (t-butoxycarbonyl) di-n-octylamine, N- (t-butoxycarbonyl) diethanolamine, N- (t-butoxycarbonyl) dicyclohexylamine, N- (t-butoxycarbonyl) diphenylamine, N- Examples thereof include t-butoxycarbonyl-4-hydroxypiperidine, Nt-amyloxycarbonyl-4-hydroxypiperidine and the like.
• the nitrogen-containing compound as the acid diffusion control agent is preferably at least one selected from the group consisting of the nitrogen-containing compound (8A) and the nitrogen-containing heterocyclic compound, and is preferably trialkylamines and aromatic amines. And at least one selected from the group consisting of morpholins, more preferably selected from the group consisting of trin-pentylamine, 2,6-diisopropylaniline and N- (undecane-1-ylcarbonyloxyethyl) morpholin. At least one is more preferred.
• a photodisintegrating base generates an acid by irradiation with radiation, and when this acid is heated at a temperature condition of 110 ° C. for 1 minute, it does not substantially dissociate the acid dissociating group in the present composition. It is preferably a compound.
• a photodisintegrating base is typically a compound in which the acid generated by exposure does not or does not easily cause an acid dissociative group dissociation reaction under conditions of use.
• an onium salt that generates a carboxylic acid, a sulfonic acid or a sulfonamide by irradiation with radiation can be preferably used.
• Preferred specific examples of the photodisintegrating base include an onium salt compound represented by the following formula (9).
• E- is an organic anion represented by R 51 -COO- , R 52 -SO 2 -N --- R 51 or R 51 - SO 3- .
• R 51 and R 52 are organic anions. , Each independently is a monovalent organic group having 1 to 30 carbon atoms.
• E ⁇ is an organic anion represented by R 51 ⁇ SO 3 ⁇ , it is attached to the carbon atom to which SO 3 ⁇ is bonded. Is not bonded to a fluorine atom.
• Z + is a radiation-sensitive onium cation.
• the monovalent organic group having 1 to 30 carbon atoms represented by R 51 is a monovalent hydrocarbon group having 1 to 30 carbon atoms, a carbon-carbon bond of the hydrocarbon group, or. At least one of the hydrogen atoms of a monovalent group ⁇ having 1 to 30 carbon atoms, a hydrocarbon group or a monovalent group ⁇ containing a divalent heteroatom-containing group at the end on the bond side is a monovalent heteroatom. Examples thereof include a monovalent group substituted with a containing group. Specific examples of these include groups similar to those exemplified as the monovalent organic group represented by R 31 , R 32 and R 33 of the above formula (4).
• the monovalent organic group having 1 to 30 carbon atoms represented by R 51 is preferably a monovalent group having a substituted or unsubstituted aromatic ring.
• the group represented by R 51 may have a partial structure represented by the above formula (7A).
• Examples of the monovalent organic group having 1 to 30 carbon atoms represented by R 52 include a substituted or unsubstituted alkyl group and a substituted or unsubstituted cycloalkyl group.
• Examples of the substituent in the substituted alkyl group include a fluoro group and the like.
• Examples of the substituent in the substituted cycloalkyl group include an alkyl group having 1 to 10 carbon atoms, a fluoro group, an iodo group and the like.
• the radiation-sensitive onium cation represented by Z + is preferably an organic cation represented by the above formula (Y-1) or formula (Y-2).
• the radiation-sensitive onium cation represented by Z + may have a specific cation structure [X] and does not have a specific cation structure [X] (that is, does it have only one substituent ⁇ ? Or it may not have a substituent ⁇ ).
• the photodisintegrating base include the following onium salts [C1] to [C4].
• the onium salts [C1] to [C4] preferably have a carboxylate anion structure or a sulfonate anion structure.
• the radiation-sensitive onium cation having two or more substituents ⁇ includes the radiation-sensitive onium cation having a partial structure represented by the above formula (1) and the above formula (1). Examples thereof include radiation-sensitive onium cations having a partial structure represented by 2).
• examples of the organic anion having an iodine group include a carboxylate anion having a partial structure represented by the above formula (3).
• the carboxylate anion in the above-mentioned example of the specific anion structure [Y] can be mentioned. However, it is not limited to the above.
• the onium cation having only one substituent ⁇ or having no substituent ⁇ is an onium cation represented by the above formula (4), and the above formula ( Examples thereof include an onium cation represented by 5) and an onium cation represented by the above formula (6).
• examples of the organic anion having no iodine group include organic anions represented by E ⁇ in the above formula (9) that do not have an iodine group.
• an organic anion represented by the following formula can be mentioned.
• the organic anion contained in the photodisintegrating base is not limited to the following structure.
• onium salts [C1] to [C4] include compounds in which the onium cation and the organic anion exemplified above are combined.
• specific examples of the onium salt [C1] include a radiation-sensitive onium cation having a partial structure represented by the above formula (1) and a carboxylate having a partial structure represented by the above formula (3).
• examples thereof include a compound composed of an anion, a radiosensitive onium cation having a partial structure represented by the above formula (2), and a compound composed of a carboxylate anion having a partial structure represented by the above formula (3). ..
• the molecular weight of the acid diffusion control agent (C) is preferably 1000 or less, more preferably 900 or less, further preferably 800 or less, and even more preferably 600 or less.
• the molecular weight of the acid diffusion control agent (C) is, for example, 100 or more, preferably 150 or more.
• the content ratio of the (C) acid diffusion control agent in the present composition is 0.1% by mass or more with respect to 100 parts by mass of the (A) polymer. Is preferable, 0.5% by mass or more is more preferable, and 1% by mass or more is further preferable.
• the content ratio of the (C) acid diffusion control agent is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, based on 100 parts by mass of the polymer (A).
• the acid diffusion control agent one type may be used alone, or two or more types may be used in combination.
• the content ratio of the acid generating compound (that is, the ratio of the total of the (B) acid generating agent and the (C) acid diffusion controlling agent) is 1 with respect to the total amount of the solid content contained in the present composition. It is preferably mass% or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more.
• the ratio of the acid-generating compound is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less with respect to the total amount of the solid content contained in the present composition. It is more preferably 8% by mass or more, and even more preferably 8% by mass or more.
• the proportion of the specific cation structure [X] in the radiation-sensitive onium cation structure contained in the present composition is preferably 10 mol% or more, more preferably 20 mol% or more, and more preferably 50 mol% or more. It is more preferably 70 mol% or more, and even more preferably 70 mol% or more.
• the proportion of the specific anion structure [Y] in the organic anion structure contained in the present composition is preferably 10 mol% or more, more preferably 20 mol% or more, and more preferably 50. It is more preferably mol% or more.
• the solvent (D) is not particularly limited as long as it is a solvent capable of dissolving or dispersing the polymer (A), the acid generator (B), and the acid diffusion control agent (C) contained if desired.
• Examples of the solvent (D) include alcohols, ethers, ketones, amides, esters, hydrocarbons and the like.
• alcohols include aliphatic monoalcohols having 1 to 18 carbon atoms such as 4-methyl-2-pentanol and n-hexanol; alicyclic monoalcohols having 3 to 18 carbon atoms such as cyclohexanol; 1, Examples thereof include polyhydric alcohols having 2 to 18 carbon atoms such as 2-propylene glycol; and partially ethers of polyhydric alcohols having 3 to 19 carbon atoms such as propylene glycol monomethyl ether.
• ethers include dialkyl ethers such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether and diheptyl ether; cyclic ethers such as tetrahydrofuran and tetrahydropyran; aromatics such as diphenyl ether and anisole. Ring-containing ether and the like can be mentioned.
• dialkyl ethers such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether and diheptyl ether
• cyclic ethers such as tetrahydrofuran and tetrahydropyran
• aromatics such as diphenyl ether and anisole. Ring-containing ether and the like can be mentioned.
• ketones examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, 2-heptanone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, and the like.
• Chain ketones such as di-iso-butyl ketone and trimethylnonanon: Cyclic ketones such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone and methylcyclohexanone: 2,4-pentandione, acetonylacetone, acetophenone, di Acetone alcohol and the like can be mentioned.
• the amides include cyclic amides such as N, N'-dimethylimidazolidinone and N-methylpyrrolidone; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methyl. Examples thereof include chain amides such as acetamide, N, N-dimethylacetamide, and N-methylpropionamide.
• esters examples include monocarboxylic acid esters such as n-butyl acetate and ethyl lactate; polyhydric alcohol carboxylates such as propylene glycol acetate; polyhydric alcohol partial ether carboxylates such as propylene glycol monomethyl ether acetate; diethyl oxalate.
• Polyvalent carboxylic acid diesters such as; carbonates such as dimethyl carbonate and diethyl carbonate; cyclic esters such as ⁇ -butyrolactone and the like can be mentioned.
• hydrocarbons examples include aliphatic hydrocarbons having 5 to 12 carbon atoms such as n-pentane and n-hexane; aromatic hydrocarbons having 6 to 16 carbon atoms such as toluene and xylene.
• the solvent preferably contains at least one selected from the group consisting of esters and ketones, and is selected from the group consisting of polyhydric alcohol partial ether carboxylates and cyclic ketones. It is more preferable to contain at least one of propylene glycol monomethyl ether acetate, ethyl lactate and cyclohexanone.
• the solvent one kind or two or more kinds can be used.
• the (E) high-fluorine-containing polymer (hereinafter, also simply referred to as “(E) polymer”) is a polymer having a larger mass content of fluorine atoms than the (A) polymer.
• the polymer (E) is contained in the present composition as, for example, a water-repellent additive.
• the polymer (E) is distinguished from the polymer (A) in that it does not have a structural unit (I).
• the fluorine atom content of the polymer (E) is not particularly limited as long as it is larger than that of the polymer (A), but is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 4% by mass or more, and 7 Mass% or more is particularly preferable.
• the fluorine atom content of the polymer (E) is preferably 60% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
• the fluorine atom content (mass%) of the polymer can be calculated from the structure of the polymer obtained by 13 C-NMR spectrum measurement or the like.
• Examples of the structural unit of the (E) polymer include the structural unit (Ea) and the structural unit (Eb) shown below.
• the polymer may have one or more structural units (Ea) and structural units (Eb), respectively.
• the structural unit (Ea) is a structural unit represented by the following formula (11a).
• the polymer can adjust the fluorine atom content by having a structural unit (Ea).
• RC is a hydrogen atom, a fluoro group, a methyl group or a trifluoromethyl group.
• G is a single bond, an oxygen atom, a sulfur atom, -CO-O-, -SO 2 -O. -NH-, -CO-NH- or -O-CO-NH-.
• RE is a monovalent fluorinated chain hydrocarbon group having 1 to 6 carbon atoms or a monovalent group having 4 to 20 carbon atoms. It is a fluorinated alicyclic hydrocarbon group.
• Examples of the monovalent fluorinated chain hydrocarbon group having 1 to 6 carbon atoms represented by RE include a trifluoromethyl group, a 2,2,2 -trifluoroethyl group, a perfluoroethyl group, and 2, 2,3,3,3-pentafluoropropyl group, 1,1,1,3,3,3-hexafluoropropyl group, perfluoron-propyl group, perfluoroisopropyl group, perfluoron-butyl group, per Examples thereof include a fluoroisobutyl group, a perfluorot-butyl group, a 2,2,3,3,4,5,5-octafluoropentyl group and a perfluorohexyl group.
• Examples of the monovalent fluorinated alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by RE include a monofluorocyclopentyl group, a difluorocyclopentyl group, a perfluorocyclopentyl group, a monofluorocyclohexyl group and a difluorocyclohexyl group. , Perfluorocyclohexylmethyl group, fluoronorbornyl group, fluoroadamantyl group, fluorobornyl group, fluoroisobornyl group, fluorotricyclodecyl group, fluorotetracyclodecyl group and the like.
• Examples of the monomer giving the structural unit (Ea) include (meth) acrylic acid ester having a fluorinated chain hydrocarbon group, (meth) acrylic acid ester having a fluorinated alicyclic hydrocarbon group, and the like. Be done. Specific examples of these include linear partially fluorinated alkyls such as, for example, 2,2,2-trifluoroethyl (meth) acrylic acid esters as (meth) acrylic acid esters having a fluorinated chain hydrocarbon group.
• Examples of the (meth) acrylic acid ester having a fluorinated alicyclic hydrocarbon group include perfluorocyclohexylmethyl (meth) acrylic acid ester, monofluorocyclopentyl (meth) acrylic acid ester, and perfluorocyclopentyl (meth) acrylic acid.
• the content ratio of the structural unit (Ea) is preferably 5 mol% or more with respect to all the structural units constituting the (E) polymer. It is more preferably 10 mol% or more, and further preferably 20 mol% or more.
• the structural unit (Eb) is a structural unit represented by the following formula (11b). Since the polymer (E) has a structural unit (Eb), the hydrophobicity is increased, so that the dynamic contact angle of the surface of the resist film formed from the present composition can be further improved.
• RF is a hydrogen atom, a fluoro group, a methyl group or a trifluoromethyl group.
• R 59 is a (s + 1) -valent hydrocarbon group having 1 to 20 carbon atoms or a hydrogen group.
• R60 is a single-bonded, divalent chain hydrocarbon group having 1 to 10 carbon atoms or a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms.
• X 12 is a divalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms.
• a 11 is an oxygen atom, -NR "-, -CO-O- * or -SO 2 -O- *.
• R " is a hydrogen atom or a monovalent organic group.
• R 61 is a hydrogen atom or a monovalent organic group. S is 1 to 1. It is an integer of 3. However, when s is 2 or 3, a plurality of R 60 , X 12 , A 11 and R 61 are the same group or different groups, respectively.)
• R 61 is a hydrogen atom, it is preferable in that the solubility of the (E) polymer in an alkaline developer can be improved.
• the monovalent organic group represented by R 61 include a hydrocarbon group having 1 to 30 carbon atoms which may have an acid dissociable group, an alkali dissociable group or a substituent.
• the content ratio of the structural unit (Eb) is preferably 5 mol% or more with respect to all the structural units constituting the (E) polymer. It is more preferably 10 mol% or more, and further preferably 20 mol% or more.
• the polymer is a structural unit containing an acid dissociative group in addition to the structural unit (Ea) and the structural unit (Eb), and is different from the structural unit (Ea) and the structural unit (Eb). (Hereinafter, also referred to as "structural unit (Ec)”) may be contained. (E) When the polymer has a structural unit (Ec), the shape of the obtained resist pattern becomes better. Examples of the structural unit (Ec) include the structural unit (II) that the polymer may have (A).
• the content ratio of the structural unit (Ec) is preferably 5 mol% or more with respect to all the structural units constituting the (E) polymer. It is more preferably 25 mol% or more, and further preferably 50 mol% or more.
• the content ratio of the structural unit (Ec) is preferably 90 mol% or less, more preferably 80 mol% or less, and 70 mol, based on all the structural units constituting the polymer (E). It is more preferably% or less.
• the content ratio of the (E) polymer in the present composition is preferably 0.1 part by mass or more with respect to 100 parts by mass of the (A) polymer. More than parts by mass is more preferable, and more than 2 parts by mass is further preferable.
• the content ratio of the (E) polymer is preferably 20 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 7 parts by mass or more with respect to 100 parts by mass of the polymer (A).
• the present composition may contain the polymer (E) alone or in combination of two or more.
• This composition has components different from the above-mentioned (A) polymer, (B) acid generator, (C) acid diffusion control agent, (D) solvent and (E) high fluorine-containing polymer (hereinafter, "others"). It may further contain (also referred to as "arbitrary component of”).
• Other optional components include, for example, a surfactant, an alicyclic skeleton-containing compound (for example, 1-adamantanane carboxylic acid, 2-adamantanone, t-butyl deoxycholic acid, etc.), a sensitizer, and an uneven distribution accelerator. And so on.
• the content ratio of other optional components in the present composition can be appropriately selected according to each component as long as the effects of the present disclosure are not impaired.
• ⁇ Manufacturing method of radiation-sensitive composition For example, in addition to (A) polymer and (B) acid generator, components such as (C) acid diffusion control agent and (D) solvent are mixed at a desired ratio to obtain the present composition.
• the resulting mixture can be produced, preferably by filtering using a filter (for example, a filter having a pore size of about 0.2 ⁇ m) or the like.
• the solid content concentration of the present composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more.
• the solid content concentration of the present composition is preferably 50% by mass or less, more preferably 20% by mass or less, still more preferably 5% by mass or less.
• the present composition thus obtained can be used as a positive pattern forming composition for forming a pattern using an alkaline developer, or as a negative pattern forming composition using a developing solution containing an organic solvent. It can also be used.
• the resist pattern forming method in the present disclosure includes a step of applying the present composition to one surface of a substrate (hereinafter, also referred to as “coating step”) and a step of exposing the resist film obtained by the above coating step (hereinafter, also referred to as “coating step”).
• coating step a step of developing the exposed resist film
• development step a step of developing the exposed resist film
• Examples of the pattern formed by the resist pattern of the present disclosure include a line-and-space pattern and a hole pattern.
• the resist pattern forming method of the present disclosure since the resist film is formed by using the present composition, it is possible to form a resist pattern having good sensitivity, a small CDU, and a small amount of development residue.
• each step will be described.
• a resist film is formed on the substrate by applying the present composition to one surface of the substrate.
• a conventionally known substrate can be used, and examples thereof include a silicon wafer, a silicon dioxide, and a wafer coated with aluminum.
• an organic or inorganic antireflection film disclosed in JP-A-6-12452 and JP-A-59-93448 may be formed on a substrate and used.
• the coating method of the present composition include rotary coating (spin coating), cast coating, roll coating and the like.
• prebaking (PB) may be performed to volatilize the solvent in the coating film.
• the temperature of PB is preferably 60 ° C.
• the temperature of PB is preferably 140 ° C. or lower, more preferably 120 ° C. or lower.
• the PB time is preferably 5 seconds or longer, more preferably 10 seconds or longer.
• the PB time is preferably 600 seconds or less, more preferably 300 seconds or less.
• the average thickness of the resist film formed is preferably 10 to 1,000 nm, more preferably 20 to 500 nm.
• the resist film obtained by the above coating step is exposed.
• This exposure is performed by irradiating the resist membrane with radiation via a photomask and, in some cases, through an immersion medium such as water.
• Radiation includes, for example, electromagnetic waves such as visible light, ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays (EUV), X-rays, and ⁇ -rays; charged particle beams such as electron beams and ⁇ -rays, depending on the line width of the target pattern. And so on.
• the radiation applied to the resist film formed by using this composition is preferably far ultraviolet, EUV or electron beam, and ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), and the like.
• EUV or electron beam is more preferred, ArF excimer laser light, EUV or electron beam is even more preferred, EUV or electron beam is even more preferred, and EUV is particularly preferred.
• PEB post-exposure baking
• the temperature of PEB is preferably 50 ° C. or higher, more preferably 80 ° C. or higher.
• the temperature of PEB is preferably 180 ° C. or lower, more preferably 130 ° C. or lower.
• the PEB time is preferably 5 seconds or longer, more preferably 10 seconds or longer.
• the PEB time is preferably 600 seconds or less, more preferably 300 seconds or less.
• the exposed resist film is developed. This makes it possible to form a desired resist pattern. After development, it is generally washed with a rinsing solution such as water or alcohol and dried.
• the developing method in the developing step may be alkaline development or organic solvent development.
• the developing solution used for development includes, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n.
• TMAH tetramethylammonium hydroxide
• pyrrole pyrrole
• piperidine choline
• 1,8-diazabicyclo- [5.4.0] -7-undecene examples thereof include an alkaline aqueous solution in which at least one of alkaline compounds such as 1,5-diazabicyclo- [4.3.0] -5-nonene is dissolved.
• the TMAH aqueous solution is preferable, and the 2.38 mass% TMAH aqueous solution is more preferable.
• the developer may be one or more of various organic solvents (for example, hydrocarbons, ethers, esters, ketones, alcohols, etc.).
• organic solvent used as the developing solution include the solvents listed as (D) solvent in the description of the present composition.
• esters and ketones are preferable as the developing solution used for organic solvent development.
• the esters acetate esters are preferable, and n-butyl acetate is more preferable.
• the ketones chain ketones are preferable, and 2-heptanone is more preferable.
• the content of the organic solvent is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 99% by mass or more.
• the components other than the organic solvent in the developing solution include water, silicone oil and the like.
• Examples of the developing method include a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), and a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle).
• dip method a method of immersing the substrate in a tank filled with a developing solution for a certain period of time
• piddle a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time
• Method a method of spraying the developer on the surface of the substrate
• spray method a method of continuing to apply the developer while scanning the developer ejection nozzle at a constant speed on the substrate rotating at a constant speed
• dynamic discharge method a constant speed
• Weight average molecular weight and number average molecular weight The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer are determined by gel permeation chromatography (GPC) of Tosoh's GPC columns (2 "G2000HXL", 1 "G3000HXL” and 1 "G4000HXL”. ) was used, and the measurement was performed under the following conditions.
• the structures of the radiation-sensitive acid generator (PAG), the acid diffusion control agent, and the high-fluorine-containing resin used for preparing the radiation-sensitive resin composition are shown below.
• PAG1 to PAG17 were synthesized by ion exchange between an ammonium salt of a sulfonic acid that gives an organic acid anion moiety and a sulfonium chloride or an iodonium chloride that gives an onium cation moiety, respectively.
• PAG1 to PAG7, PAG9, PAG11 to PAG14, and PAG17 are radiation-sensitive acid generators having a specific cation structure [X].
• the number of substituents ⁇ of PAG1 is 2, and the number of substituents ⁇ of PAG2 is 2.
• PAGs 1 to 7 and PAGs 10 to 16 are radiation-sensitive acid generators having a specific anion structure [Y].
• Acid diffusion control agent The structures of the acid diffusion regulators (Q-1 to Q-8) used in the following examples are as follows. Note that Q-2, Q-4, and Q-7 are acid diffusion control agents having a specific cation structure [X]. Further, Q-2, Q-3, Q-5, Q-7, and Q-8 are acid diffusion control agents having a specific anion structure [Y].
• EUV scanner (ASML "NXE3300" (NA0.33, ⁇ 0.9 / 0.6, quadrupole illumination, wafer size is 46 nm pitch, + 20% bias hole pattern mask)) was exposed using.
• PEB was performed on a hot plate at 120 ° C. for 60 seconds, and development was performed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to form a resist pattern having 23 nm holes and a 46 nm pitch.
• TMAH tetramethylammonium hydroxide
• the exposure amount for forming the resist pattern of the 23 nm hole and 46 nm pitch was defined as the optimum exposure amount (Eop), and the optimum exposure amount was defined as the sensitivity (mJ / cm 2 ).
• the radiation-sensitive resin compositions of Examples 1 to 20 had good sensitivity and CDU performance, and had a small amount of development residue.
• the radiation-sensitive resin compositions of Examples 3 to 20 containing the radiation-sensitive onium cation having a total number of fluorogroups and fluoroalkyl groups of 3 or more as the specific cation [X] have a development residue of 10 or less. , "A" or "B". Further, the effect of reducing the development residue was particularly excellent when the total number of fluoro groups and fluoroalkyl groups in the specific cation [X] was 4 or more.
• the radiation-sensitive resin composition and the resist pattern forming method described above it is possible to form a resist pattern having good sensitivity to exposure light and excellent CDU performance and development residue suppressing property. Therefore, these can be suitably used for processing processes of semiconductor devices, which are expected to be further miniaturized in the future.

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