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
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative 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
• • 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
  • G03F7/20—Exposure; Apparatus therefor

Definitions

• Photolithography technology uses a resist composition to form fine circuits in semiconductor elements.
• the typical procedure is to first expose a coating of the resist composition to radiation through a mask pattern, generating acid, which then undergoes a chemical reaction involving the acid, creating a difference in solubility in the developer (dissolution contrast) between exposed and unexposed areas, thereby forming a resist pattern on the substrate.
• Patent Document 1 discloses a resist composition containing a resin having a repeating unit with an internal salt structure.
• Patent Document 1 discloses that by introducing a repeating unit with an internal salt structure into the resin, a quencher is uniformly dispersed within the surface of the resist film, and acid is captured in the unexposed areas.
• the present disclosure has been made in consideration of the above problems, and has as its main objective the provision of a radiation-sensitive composition and a method for forming a resist pattern that can achieve both high sensitivity and LWR performance, and can suppress the occurrence of development defects.
• the present inventors have discovered that the above problem can be solved by forming a radiation-sensitive composition containing a polymer having a specific betaine structure and a radiation-sensitive acid generator having an iodine group. Specifically, the present disclosure provides the following means.
• the present disclosure provides a radiation-sensitive composition containing: (A) a polymer including a structural unit represented by the following formula (1); and (B) an onium salt compound including an organic anion and a cation, wherein the organic anion, the cation, or both of them have an iodine group, and which generates an acid upon exposure to radiation: (In formula (1), R 1 , R 2 and R 3 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms or a halogenated alkyl group having 1 to 6 carbon atoms.
• a 1 is a single bond, -O-, -CO-, -COO-, -NH-, -CONH- or * 1 -Ar 1 -A 3 -.
• Ar 1 is a divalent aromatic ring group.
• a 3 is a single bond, -O-, -CO-, -COO-, -NH- or -CONH-.
• "* 1 " represents a bond to the carbon atom to which R 3 is bonded.
• B 1 is a single bond or a divalent organic group having 1 or more carbon atoms bonded to E + in formula (1) via a carbon atom.
• E + is a divalent group having an ammonium cation structure or a phosphonium cation structure.
• B 2 is a divalent group having E + and D D - is a divalent organic group having one or more carbon atoms bonded to each of the - via the same or different carbon atoms.
• D - is a monovalent group having an anionic structure.
• the present disclosure provides a method for forming a resist pattern, comprising the steps of applying the radiation-sensitive composition onto a substrate to form a resist film, exposing the resist film to light, and developing the exposed resist film.
• a radiation-sensitive composition that contains a polymer containing a structural unit represented by the above formula (1) and an onium salt compound in which one or both of the organic anion and cation have an iodine group, it is possible to exhibit high sensitivity and excellent LWR performance during resist pattern formation, and to reduce the occurrence of development defects.
• the radiation-sensitive composition of the present disclosure contains a polymer including a structural unit having a betaine structure (hereinafter also referred to as “polymer (A)”), and a radiation-sensitive acid generator having an iodine group (hereinafter also referred to as “compound (B)”).
• the polymer (A) may constitute the base resin of the radiation-sensitive composition, or may constitute a component different from the base resin.
• An example of a component different from the base resin is a polymer having a higher mass content of fluorine atoms than the base resin (hereinafter, also referred to as a "high fluorine content polymer").
• the "base resin” refers to a polymer component that accounts for 50 mass% or more of the total amount of solids contained in the composition.
• the polymer (A) is preferably a high fluorine content polymer, since it exhibits high sensitivity and excellent LWR performance during resist pattern formation, and can exert an excellent effect of reducing development defects. Below, we will first explain in detail each component contained in the composition, and the components that are optionally blended as necessary.
• hydrocarbon group includes linear hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups.
• linear hydrocarbon group refers to linear and branched hydrocarbon groups that do not include a cyclic structure and are composed only of linear structures. However, linear hydrocarbon groups may be saturated or unsaturated.
• alicyclic hydrocarbon group refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. However, an alicyclic hydrocarbon group does not have to be composed only of an alicyclic hydrocarbon structure and may include groups that have a linear structure as part of it.
• aromatic hydrocarbon group refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure.
• an aromatic hydrocarbon group does not have to be composed only of an aromatic ring structure and may include a linear structure or an alicyclic hydrocarbon structure as part of it.
• Aromatic ring group refers to an n-valent group obtained by removing n hydrogen atoms (where n is an integer of 1 or more) from the ring portion of a substituted or unsubstituted aromatic ring.
• “Aromatic ring” includes aromatic hydrocarbon rings and aromatic heterocycles.
• the expression "substituted or unsubstituted p-valent hydrocarbon group (where p is an integer of 1 or more)” includes p-valent hydrocarbon groups (i.e., unsubstituted p-valent hydrocarbon groups) and groups in which p hydrogen atoms have been removed from the hydrocarbon structural portion of a substituted hydrocarbon group.
• fluoroalkyl groups are "substituted monovalent hydrocarbon groups”
• fluoroalkanediyl groups are "substituted divalent hydrocarbon groups”. The same applies to other groups to which "substituted or unsubstituted" is added.
• “Bridged structure” refers to a polycyclic ring structure in which two carbon atoms that are not adjacent to each other are bonded by a bond chain containing one or more carbon atoms.
• “Fused ring structure” refers to a polycyclic ring structure in which multiple rings share an edge (a bond between two adjacent carbon atoms).
• “Spiro ring structure” refers to a polycyclic ring structure in which two rings share one atom.
• a spiro ring structure may be formed by combining single ring structures, and may include a bridged structure or a fused ring structure.
• Organic group refers to an atomic group formed by removing any hydrogen atom from a compound that contains carbon (i.e., an organic compound).
• (Meth)acrylic is a term that includes “acrylic” and “methacrylic”.
• Structure unit refers to a unit that mainly constitutes the main chain structure, and is a structural unit of a chemical structure that is included in at least two or more of the main chain structure.
• the polymer (A) contains a structural unit represented by the following formula (1) (hereinafter also referred to as a "first structural unit").
• R 1 , R 2 and R 3 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms or a halogenated alkyl group having 1 to 6 carbon atoms.
• a 1 is a single bond, -O-, -CO-, -COO-, -NH-, -CONH- or * 1 -Ar 1 -A 3 -.
• Ar 1 is a divalent aromatic ring group.
• a 3 is a single bond, -O-, -CO-, -COO-, -NH- or -CONH-.
• "* 1 " represents a bond to the carbon atom to which R 3 is bonded.
• B 1 is a single bond or a divalent organic group having 1 or more carbon atoms bonded to E + in formula (1) via a carbon atom.
• E + is a divalent group having an ammonium cation structure or a phosphonium cation structure.
• B 2 is a divalent group having E + and D D - is a divalent organic group having one or more carbon atoms bonded to each of the - via the same or different carbon atoms.
• D - is a monovalent group having an anionic structure.
• the alkyl group having 1 to 6 carbon atoms represented by R 1 , R 2 or R 3 may be linear or branched.
• the halogen atom contained in the halogenated alkyl group having 1 to 6 carbon atoms represented by R 1 , R 2 or R 3 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• R 1 and R 2 are preferably a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group having 1 to 3 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms, and a hydrogen atom is particularly preferred.
• R3 is preferably a hydrogen atom or a methyl group.
• examples of the divalent aromatic ring group represented by Ar 1 include a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalene group, etc.
• substituent include a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, etc.
• B 1 is a divalent organic group having 1 or more carbon atoms bonded to E + in the above formula (1) via a carbon atom
• examples of the divalent organic group include a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, and a divalent group containing -O-, -CO-, -COO-, -NH- or -CONH- between the carbon-carbon bonds in the substituted or unsubstituted hydrocarbon group.
• divalent hydrocarbon groups having 1 to 20 carbon atoms include divalent linear hydrocarbon groups having 1 to 20 carbon atoms, divalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms.
• Divalent chain hydrocarbon groups having 1 to 20 carbon atoms include linear or branched divalent saturated hydrocarbon groups having 1 to 20 carbon atoms, and linear or branched divalent unsaturated hydrocarbon groups having 2 to 20 carbon atoms. Of these, linear or branched divalent saturated hydrocarbon groups having 1 to 20 carbon atoms are preferred, and linear or branched divalent saturated hydrocarbon groups having 1 to 10 carbon atoms are more preferred.
• Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include groups in which any two hydrogen atoms have been removed from an alicyclic monocyclic hydrocarbon or alicyclic polycyclic hydrocarbon having 3 to 20 carbon atoms.
• Examples of the ring contained in the alicyclic monocyclic hydrocarbon include saturated aliphatic rings such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane; and unsaturated aliphatic rings such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and cyclodecene.
• Examples of the ring contained in the alicyclic polycyclic hydrocarbon include saturated aliphatic rings such as norbornane, bicyclo[2.2.2]octane, adamantane, and tricyclo[5.2.1.0 2,6 ]decane; and unsaturated aliphatic rings such as norbornene.
• Divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include aromatic rings such as benzene, naphthalene, anthracene, indene, and fluorene, or groups in which any two hydrogen atoms have been removed from a structure in which a chain hydrocarbon or alicyclic hydrocarbon is bonded to the aromatic ring.
• examples of the substituent on B1 or B2 include a halogen atom, a hydroxyl group, a cyano group, a nitro group, a halogenated alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkoxycarbonyl group having 2 to 6 carbon atoms.
• B 1 is preferably a divalent organic group having 1 or more carbon atoms bonded to E + in formula (1) via a carbon atom.
• the divalent organic group represented by each of B 1 and B 2 preferably has a chain structure, specifically, it is preferably a substituted or unsubstituted divalent chain hydrocarbon group having 1 to 20 carbon atoms, or a divalent group containing -O-, -CO-, -COO-, -NH- or -CONH- between the carbon-carbon bonds of the chain hydrocarbon group, and among these, a chain structure having 1 to 10 carbon atoms is more preferable.
• B1 when B1 is "bonded to E + through a carbon atom,” it means that E + (more specifically, a nitrogen atom or phosphorus atom in E + ) is directly bonded to a carbon atom in B1 .
• B2 when B2 is "bonded to E + and D- through a carbon atom,” it means that E + (more specifically, a nitrogen atom or phosphorus atom in E + ) is directly bonded to a carbon atom in B2 , and D- is directly bonded to a carbon atom in B2 .
• the carbon atom in B1 that is bonded to E + , the carbon atom in B2 that is bonded to E + , and the carbon atom in B2 that is bonded to D- may each be a primary carbon atom, a secondary carbon atom, or a tertiary carbon atom, and may be adjacent to an oxygen atom or a heteroatom-containing group such as a carbonyl group in B1 or B2 .
• E + is a divalent group having an ammonium cation structure or a phosphonium cation structure.
• the divalent group represented by E + include structures represented by the following formula (e-1), formula (e-2) or formula (e-3).
• R6 and R7 are each independently a monovalent hydrocarbon group, or R6 and R7 taken together represent an aliphatic heterocyclic structure together with the nitrogen atom to which R6 and R7 are bonded.
• R8 and R9 are each independently a monovalent hydrocarbon group, or R8 and R9 taken together represent a heterocyclic structure together with the phosphorus atom to which R8 and R9 are bonded.
• "*" represents a bond.
• examples of the monovalent hydrocarbon group represented by R 6 , R 7 , R 8 or R 9 include a monovalent chain hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.
• Examples of monovalent chain hydrocarbon groups having 1 to 10 carbon atoms include linear or branched saturated hydrocarbon groups having 1 to 10 carbon atoms, and linear or branched unsaturated hydrocarbon groups having 1 to 10 carbon atoms. Of these, linear or branched saturated hydrocarbon groups having 1 to 10 carbon atoms are preferred.
• Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include groups in which one hydrogen atom has been removed from a saturated alicyclic hydrocarbon, an unsaturated alicyclic hydrocarbon, or an alicyclic polycyclic hydrocarbon having 3 to 20 carbon atoms. Specific examples of these alicyclic hydrocarbons include the alicyclic monocyclic hydrocarbons and alicyclic polycyclic hydrocarbons exemplified in the description of B1 and B2 in the above formula (1). Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include groups in which one hydrogen atom has been removed from an aromatic ring exemplified in the description of B1 and B2 in the above formula (1).
• Examples of the aliphatic heterocyclic structure formed by combining R 6 and R 7 together with the nitrogen atom to which R 6 and R 7 are bonded include groups in which a hydrogen atom is removed from a nitrogen atom constituting a nitrogen-containing aliphatic heterocyclic ring (e.g., a piperidine ring, etc.).
• Examples of the ring structure formed by combining R 8 and R 9 together with the phosphorus atom to which R 8 and R 9 are bonded include groups in which a hydrogen atom is removed from a phosphorus atom constituting a phosphorus-containing heterocyclic ring (e.g., a phosphinane ring, a phosphole ring, etc.).
• the nitrogen-containing aliphatic heterocyclic structure and the phosphorus-containing heterocyclic structure may each have a substituent such as an alkyl group in the ring.
• the divalent group represented by E 2 + preferably has an ammonium cation structure, and among these, a group represented by the above formula (e-1) or formula (e-2) is preferable.
• D - is a monovalent group having an anionic structure.
• D - include “-COO - ", “-SO 3 - “, “-PO 3 - “, “-POO - “ and “-O - “.
• D - is preferably a carboxylate structure (-COO - ) or a sulfonate structure (-SO 3 - ) in that it is possible to obtain a sufficient effect of improving LWR performance and reducing development defects while increasing the sensitivity of the present composition.
• a sulfonate structure is more preferable from the viewpoint of sensitivity
• a carboxylate structure is more preferable from the viewpoint of obtaining a sufficient effect of improving LWR performance and reducing development defects.
• the betaine structure of the first structural unit is preferably an intramolecular salt structure of an ammonium cation structure and a carboxylate structure or a sulfonate structure.
• Specific examples of the first structural unit include structural units represented by the following formula (1-1) or (1-2).
• R 1 , R 2 , R 3 , A 1 , B 1 and B 2 are each defined as in formula (1) above.
• R 6 and R 7 are each defined as in formula (e-1) above.)
• R 1 B is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, or a halogenated alkyl group having 1 to 6 carbon atoms.
• the content ratio of the first structural unit in the (A) polymer is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 5 mol% or more, based on the total structural units constituting the (A) polymer, from the viewpoint of fully obtaining the effect of increasing the sensitivity of the radiation-sensitive composition and improving the LWR performance of the resist film. Also, the content ratio of the first structural unit is preferably 55 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less, based on the total structural units constituting the (A) polymer, from the viewpoint of exhibiting good LWR performance in the obtained resist film.
• the (A) polymer may contain only one type of the first structural unit, or may contain two or more types.
• the polymer (A) may further include, in addition to the first structural unit, a structural unit different from the first structural unit (hereinafter also referred to as "other structural units").
• other structural units include the following second to fifth structural units.
• the polymer (A) may further contain a structural unit having a fluorine atom (hereinafter also referred to as the "second structural unit").
• the second structural unit a structural unit having a fluorine atom
• the polymer (A) can be unevenly distributed in the surface layer of the resist film relative to the base resin, and the water repellency of the surface of the resist film can be increased during immersion exposure.
• the second structural unit differs from the first structural unit in that it does not have an intramolecular salt structure.
• the fluorine atom content of the polymer (A) is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 4% by mass or more, and particularly preferably 7% by mass or more.
• the fluorine atom content of the polymer (A) 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 (for example, the ratio of the carbon atoms derived from the monomer that provides the first structural unit to the carbon atoms derived from the monomer that provides the second structural unit) determined by 13C-NMR spectrum measurement or the like.
• the second structural unit may be, for example, a structural unit having a fluorinated aliphatic hydrocarbon structure (hereinafter also referred to as “structural unit (fa)”), a structural unit having an alkali-soluble group or an alkali-dissociable group and a fluorine atom (hereinafter also referred to as “structural unit (fb)").
• structural unit (fa) a structural unit having a fluorinated aliphatic hydrocarbon structure
• structural unit (fb) a structural unit having an alkali-soluble group or an alkali-dissociable group and a fluorine atom
• the alkali-dissociable group refers to a group that dissociates under the action of an alkali to increase the solubility in an alkaline developer.
• the (A) polymer may contain only one of the structural units (fa) and (fb), or may contain both the structural units (fa) and (fb).
• the second structural unit at least one selected from the group consisting of the structural units (fa) and (fb) can be preferably used.
• a structural unit having a fluorinated aliphatic hydrocarbon structure together with an alkali-soluble group or an alkali-dissociable group is classified as a structural unit (fb).
• Structural unit (fa) An example of the structural unit (fa) is a structural unit represented by the following formula (7-1): When the polymer (A) contains the structural unit (fa), the fluorine atom content in the polymer (A) can be adjusted.
• R C 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, -COO-, -SO 2 -O-NH-, -CONH-, or -O-CO-NH-.
• R E is a monovalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms, a monovalent group in which some of the methylene groups in the fluorinated chain hydrocarbon group are replaced with oxygen atoms, sulfur atoms, -COO-, or -CONH-, or a monovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms.
• R C is preferably a hydrogen atom or a methyl group, more preferably a methyl group, from the viewpoint of copolymerizability of the monomer that gives the structural unit (fa).
• G is preferably a single bond or -COO-, more preferably -COO-, from the viewpoint of copolymerizability of the monomer that gives the structural unit (fa).
• Examples of the monovalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms represented by R E include a linear or branched alkyl group having 1 to 20 carbon atoms in which some or all of the hydrogen atoms have been substituted with fluorine atoms.
• Examples of the monovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R E include a monocyclic or polycyclic alicyclic hydrocarbon group having 3 to 20 carbon atoms (for example, a group in which one hydrogen atom has been removed from the alicyclic monocyclic hydrocarbon or alicyclic polycyclic hydrocarbon exemplified in the description of B 1 and B 2 in the above formula (1)) in which some or all of the hydrogen atoms have been substituted with fluorine atoms.
• R E is preferably a monovalent fluorinated chain hydrocarbon group or a monovalent group in which a methylene group in the fluorinated chain hydrocarbon group is partially replaced with an oxygen atom, a sulfur atom, -COO- or -CONH-, and more preferably a monovalent fluorinated alkyl group or a monovalent group in which a methylene group in the fluorinated alkyl group is partially replaced with an oxygen atom, a sulfur atom, -COO- or -CONH-.
• R C is a hydrogen atom, a fluoro group, a methyl group, or a trifluoromethyl group.
• the content of the structural unit (fa) is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 50 mol% or more, based on all the structural units constituting the (A) polymer.
• the content of the structural unit (fa) is preferably 99 mol% or less, more preferably 97 mol% or less, and even more preferably 95 mol% or less, based on all the structural units constituting the (A) polymer.
• Structural unit (fb) An example of the structural unit (fb) is a structural unit represented by the following formula (7-2): When the (A) polymer contains the structural unit (fb), the water repellency of the resist film during immersion exposure is enhanced, while the solubility in an alkaline developer is improved, thereby further suppressing the occurrence of development defects.
• R 2 F is a hydrogen atom, a fluoro group, a methyl group, or a trifluoromethyl group.
• a 2 is a single bond, -O-, -CO-, -COO-, -NH-, or -CONH-.
• R 59 is an (s+1)-valent hydrocarbon group having 1 to 20 carbon atoms, or a group in which an oxygen atom, a sulfur atom, -NR 62 -, a carbonyl group, -CO-O-, or -CO-NH- is bonded to the end of the hydrocarbon group on the R 60 side.
• R 62 is a hydrogen atom or a monovalent organic group.
• R 60 is a single bond or a divalent organic group having 1 to 20 carbon atoms.
• X 12 is a single bond, a hydrocarbon group having 1 to 20 carbon atoms, or a divalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms.
• a 11 is an oxygen atom, -NR 63 -, -CO-O-*, or -SO 2 -O-*.
• R 63 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
• "*" represents a bond to R 61.
• R 61 is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms.
• s is an integer of 1 to 3. However, when s is 2 or 3, multiple R 60 , X 12 , A 11 and R 61 are each the same or different.
• R 61 is a hydrogen atom
• a 11 is an oxygen atom, -CO-O-* or -SO 2 -O-*.
• X 12 is a single bond, a hydrocarbon group having 1 to 20 carbon atoms, or a divalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms.
• a 11 is an oxygen atom
• X 12 is a fluorinated hydrocarbon group having a fluorine atom or a fluoroalkyl group on the carbon atom to which A 11 is bonded.
• R 60 is a single bond or a divalent organic group having 1 to 20 carbon atoms.
• the structural unit (fb) having an alkali-soluble group is preferably a structural unit containing a hydroxyl group bonded to a fluorinated saturated chain hydrocarbon structure.
• R 61 is a hydrogen atom
• a 11 is an oxygen atom
• X 12 is a divalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms, and more preferably that X 12 is a fluorinated hydrocarbon group in which a fluorine atom or a fluoroalkyl group is bonded to the carbon atom to which A 11 is bonded (for example, a 1,1,1,3,3,3-hexafluoro-2,2-methanediyl group).
• R 61 is a monovalent organic group having 1 to 30 carbon atoms, and A 11 is an oxygen atom, -NR 63 -, -CO-O-* or -SO 2 -O-*.
• X 12 is a single bond or a divalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms.
• R 60 is a single bond or a divalent organic group having 1 to 20 carbon atoms.
• a 11 is -CO-O-* or -SO 2 -O-*
• X 12 or R 61 has a fluorine atom bonded to the carbon atom bonded to A 11 or to a carbon atom adjacent thereto.
• R 59 is a structure in which a carbonyl group is bonded to the end of a hydrocarbon group having 1 to 20 carbon atoms on the R 60 side, and R 61 is an organic group having a fluorine atom, or X 12 and R 60 are single bonds
• R 59 is a hydrocarbon group having 1 to 20 carbon atoms
• R 61 is a structure in which a carbonyl group is bonded to the end of A 11 , and a fluorine atom is bonded to the carbon atom adjacent to the carbonyl group.
• the structural unit (fb) has an alkali dissociable group, so that the surface of the resist film can be changed from hydrophobic to hydrophilic in an alkali development step. This can increase the water repellency of the resist film during immersion exposure, while increasing the affinity of the resist film with the developer during development, thereby more efficiently suppressing development defects.
• a 11 is preferably -CO-O-* or an oxygen atom, and generates a carboxyl group or a hydroxyl group by the action of an alkali.
• R F is a hydrogen atom, a fluoro group, a methyl group, or a trifluoromethyl group.
• the content of the structural unit (fb) is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 50 mol% or more, based on all the structural units constituting the (A) polymer.
• the content of the structural unit (fb) is preferably 99 mol% or less, more preferably 97 mol% or less, and even more preferably 95 mol% or less, based on all the structural units constituting the (A) polymer.
• examples of the second structural unit include a structural unit having an acid dissociable group together with a fluorine atom.
• a structural unit having an acid dissociable group together with a fluorine atom (excluding fluorine atoms directly bonded to the main chain and fluorine atoms in trifluoromethyl groups) is classified as a second structural unit.
• the (A) polymer contains the structural unit (fb) as the second structural unit.
• the content ratio of the second structural unit in the (A) polymer is preferably 45 mol% or more, more preferably 50 mol% or more, and even more preferably 60 mol% or more, based on all structural units constituting the (A) polymer. Also, when the (A) polymer is a high fluorine content polymer, the content ratio of the second structural unit is preferably 99 mol% or less, more preferably 97 mol% or less, and even more preferably 95 mol% or less, based on all structural units constituting the (A) polymer. By setting the content ratio of the second structural unit within the above range, it is possible to sufficiently increase the water repellency of the resist film during immersion exposure while sufficiently suppressing the occurrence of development defects.
• the content of the second structural unit is preferably 40 mol % or less, more preferably 30 mol % or less, and even more preferably 20 mol % or less, based on the total structural units constituting the (A) polymer.
• the (A) polymer may contain only one type of the second structural unit, or may contain two or more types.
• the (A) polymer may further contain a structural unit containing an acid dissociable group (excluding structural units corresponding to the first structural unit or the second structural unit.
• the acid dissociable group is a group that substitutes a hydrogen atom of an acid group such as a carboxy group or a hydroxy group, and is a group that dissociates under the action of an acid.
• the acid dissociable group is dissociated by the acid generated by exposure of the composition to generate an acid group, and the solubility of the polymer component in the developer changes. This can impart good lithography properties to the composition.
• the third structural unit is not particularly limited as long as it has an acid-dissociable group.
• Examples of the third structural unit include a structural unit represented by the following formula (i-1) (hereinafter also referred to as “structural unit (3-1)”) and a structural unit represented by the following formula (i-2) (hereinafter also referred to as “structural unit (3-2)").
• R 42 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
• L 3 is a single bond, a substituted or unsubstituted phenylene group, **-COO-Ar 1 -, or **-CONH-Ar 1 -.
• Ar 1 is a substituted or unsubstituted phenylene group. "**" represents a bond to the carbon atom to which R 42 is bonded.
• R 43 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• R 44 and R 45 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic heterocyclic group, or R 44 and R 45 taken together represent an alicyclic hydrocarbon structure having 3 to 20 carbon atoms formed together with the carbon atom to which R 44 and R 45 are bonded.
• R 43 is a hydrogen atom
• R 44 and R Either or both of R 43 , R 44 and R 45 are, independently of each other, a monovalent unsaturated hydrocarbon group, a monovalent aromatic heterocyclic group, or R 44 and R 45 taken together represent an alicyclic unsaturated hydrocarbon structure having 3 to 20 carbon atoms constituted together with the carbon atom to which R 44 and R 45 are bonded. At least a portion of the hydrogen atoms possessed by R 43 , R 44 and R 45 may be substituted with a halogen atom or an alkoxy group.
• R 46 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
• L 4 is a single bond, -COO-, or -CONH-.
• R 47 , R 48 , and R 49 are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent oxyhydrocarbon group having 1 to 20 carbon atoms.
• R 40 is a hydroxyl group, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or an oxyhydrocarbon group having 1 to 10 carbon atoms.
• u is an integer of 0 to 4. At least a portion of the hydrogen atoms possessed by R 47 , R 48 , and R 49 may be substituted with a halogen atom or an alkoxy group.
• R 42 is preferably a hydrogen atom or a methyl group, more preferably a methyl group, from the viewpoint of copolymerizability of the monomer that gives the structural unit (3-1).
• R 46 is preferably a hydrogen atom, from the viewpoint of copolymerizability of the monomer that gives the structural unit (3-2).
• Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 43 to R 45 and R 47 to R 49 include a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Specific examples of these include monovalent hydrocarbon groups corresponding to the divalent hydrocarbon groups having 1 to 20 carbon atoms exemplified in the description of B 1 and B 2 in the above formula (1).
• Examples of the monovalent unsaturated hydrocarbon group represented by R 44 or R 45 include the monocyclic or polycyclic alicyclic unsaturated hydrocarbon groups and aromatic hydrocarbon groups exemplified in the description of B 1 and B 2 in the above formula (1).
• Examples of the monovalent aromatic heterocyclic group include a furyl group and a thienyl group.
• the alicyclic hydrocarbon structure having 3 to 20 carbon atoms constituted by combining R 44 and R 45 together with the carbon atom to which R 44 and R 45 are bonded may be saturated or unsaturated.
• Examples of the alicyclic hydrocarbon structure include groups in which one hydrogen atom has been removed from the alicyclic monocyclic hydrocarbons or alicyclic polycyclic hydrocarbons exemplified in the description of B 1 and B 2 in the above formula (1).
• An alkyl group, an alkoxy group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom
• a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom
• Examples of the monovalent oxyhydrocarbon group having 1 to 20 carbon atoms represented by R 47 to R 49 include those which contain an oxygen atom at the bond-side terminal of the monovalent hydrocarbon group having 1 to 20 carbon atoms exemplified by R 43 to R 45 and R 47 to R 49 above.
• R 47 to R 49 are preferably a chain hydrocarbon group or a cycloalkyloxy group.
• examples of the substituent introduced into the phenylene group include a hydroxyl group, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an oxyhydrocarbon group having 1 to 10 carbon atoms, an acyl group, and an acyloxy group.
• structural unit (3-1) examples include structural units represented by the following formulas: (In the formula, R 42 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.)
• R 46 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
• the content of the third structural unit in the (A) polymer is preferably 2 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on the total structural units constituting the (A) polymer.
• the content of the third structural unit is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 50 mol% or less, based on the total structural units constituting the (A) polymer.
• the (A) polymer may further contain a structural unit having a hydroxyl group bonded to an aromatic ring (excluding the structural units corresponding to the first to third structural units; hereinafter, also referred to as the "fourth structural unit").
• the (A) polymer preferably contains the fourth structural unit in that it can improve the etching resistance and the difference in developer solubility (dissolution contrast) between exposed and unexposed areas.
• a polymer having the fourth structural unit can be preferably used in pattern formation using exposure to radiation having a wavelength of 50 nm or less, such as electron beams or EUV.
• examples of the aromatic ring to which the hydroxyl group is bonded include a benzene ring, a naphthalene ring, and an anthracene ring. Of these, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred.
• the number and bonding positions of the hydroxyl groups bonded to the aromatic ring are not particularly limited. The number of hydroxyl groups bonded to the aromatic ring is preferably 1 to 3, and more preferably 1 or 2. Examples of the fourth structural unit include a structural unit represented by the following formula (ii).
• R P1 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
• L 2 is a single bond, -O-, -CO-, -COO-, or -CONH-.
• Y 3 is a monovalent group having a hydroxyl group bonded to an aromatic ring.
• R P1 is preferably a hydrogen atom or a methyl group from the viewpoint of copolymerizability of the monomer that provides the fourth structural unit, and L 2 is preferably a single bond or -COO-.
• R P1 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
• the content ratio of the fourth structural unit in the (A) polymer is preferably 2 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on the total structural units constituting the (A) polymer.
• the content ratio of the fourth structural unit is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, based on the total structural units constituting the (A) polymer.
• the (A) polymer may contain only one type of fourth structural unit, or may contain two or more types.
• the (A) polymer may contain a structural unit in which an acid-dissociable group and a hydroxyl group are bonded to the same or different aromatic rings.
• a structural unit in which an acid-dissociable group and a hydroxyl group are bonded to the same or different aromatic rings is classified as a third structural unit.
• the (A) polymer may further contain a structural unit having a lactone structure, a cyclic carbonate structure, a sultone structure, or a ring structure combining two or more of these (hereinafter also referred to as "fifth structural unit").
• a structural unit having a lactone structure, a cyclic carbonate structure, a sultone structure, or a ring structure combining two or more of these hereinafter also referred to as "fifth structural unit”
• the solubility in the developer can be adjusted, and as a result, the lithography properties of the present composition can be further improved, which is preferable.
• the adhesion between the resist film obtained by using the present composition and the substrate can be improved.
• Examples of the fifth structural unit include a structural unit represented by the following formula.
• R L1 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
• the content of the fifth structural unit is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, based on the total structural units constituting the (A) polymer.
• the content of the fifth structural unit is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less, based on the total structural units constituting the (A) polymer.
• other structural units include, for example, the following structural units.
• the content ratio of these structural units can be appropriately set according to each structural unit within a range that does not impair the effects of the present disclosure.
• a structural unit having an alcoholic hydroxyl group (excluding the structural units corresponding to the first to fifth structural units).
• a structural unit containing a partial structure that generates an acid in the composition upon exposure to light for example, a structural unit containing a partial structure consisting of a triarylsulfonium cation and an organic anion, a structural unit containing a partial structure consisting of a diaryliodonium cation and an organic anion).
• a structural unit 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 units containing a non-acid dissociable hydrocarbon group for example, a structural unit derived from styrene, a structural unit derived from vinylnaphthalene, a structural unit derived from n-pentyl (meth)acrylate, or a structural unit derived from indene
• Examples of the structural unit containing a partial structure that generates an acid in the present composition upon exposure include a structural unit containing a partial structure that generates a sulfonic acid (including a sulfonic acid group) in the present composition upon exposure; and a structural unit containing a partial structure that generates a carboxylic acid (including a carboxylic acid group) in the present composition upon exposure.
• the sixth structural unit is preferably a structural unit in which a sulfonate anion (-SO 3 - ) is bonded to the main chain of the polymer via a linking group and a radiation-sensitive onium cation forms a counter ion (hereinafter referred to as "structural unit (6-1)"), or a structural unit in which a carboxylate anion (-CO 2 - ) is bonded to the main chain of the polymer via a linking group and a radiation-sensitive onium cation forms a counter ion (hereinafter referred to as "structural unit (6-2)").
• the polymer (A) may contain the structural unit (6-1) and the structural unit (6-2) as the sixth structural unit.
• the sixth structural unit preferably has an iodine group in that the sensitivity of the present composition can be further increased.
• the weight average molecular weight (Mw) of the (A) polymer is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 3,000 or more, and even more preferably 4,000 or more.
• the Mw of the (A) polymer is preferably 50,000 or less, more preferably 30,000 or less, even more preferably 20,000 or less, and even more preferably 18,000 or less.
• Mw/Mn The ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) of the (A) polymer by GPC (Mw/Mn) is preferably 5.0 or less, more preferably 3.0 or less, and even more preferably 2.0 or less. In addition, Mw/Mn is usually 1.0 or more.
• the content of the (A) polymer in the composition is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1 mass% or more, based on the total amount of solids contained in the composition (i.e., the total amount of the composition excluding the solvent contained in the composition).
• the content of the (A) polymer is preferably 20 mass% or less, more preferably 15 mass% or less, and even more preferably 12 mass% or less, based on the total amount of solids contained in the composition.
• the content of the (A) polymer in the composition is preferably 70 mass% or more, more preferably 75 mass% or more, and even more preferably 80 mass% or more, based on the total amount of solids contained in the composition (i.e., the total mass of components other than the solvent component contained in the composition).
• the content of the (A) polymer is preferably 99 mass% or less, more preferably 98 mass% or less, and even more preferably 95 mass% or less, based on the total amount of solids contained in the composition.
• One type of (A) polymer may be used alone, or two or more types may be used in combination.
• the method for synthesizing the polymer (A) is not particularly limited.
• the polymer can be synthesized by polymerizing the monomers that provide each structural unit in an appropriate solvent using a radical polymerization initiator or the like.
• the compound (B) is an onium salt composed of a cation and an organic anion, and one or both of the cation and the organic anion constituting the onium salt have an iodine group.
• the compound (B) functions as a radiation-sensitive acid generator in the present composition.
• the organic anion that constitutes the onium salt is usually an anion formed by removing a proton from the acid group of an organic acid.
• an onium salt compound that serves as a radiation-sensitive acid generator the radiation-sensitive onium cation is decomposed by the action of radiation to liberate an organic anion, which then bonds with hydrogen extracted from a component contained in the composition (for example, the radiation-sensitive acid generator itself or a solvent) to generate an acid derived from the organic anion.
• the (B) compound may be incorporated in the composition as a radiation-sensitive acid generator, an acid diffusion controller (more specifically, a photodegradable base), or both an acid generator and an acid diffusion controller.
• the term "acid generator” refers to a component that, upon exposure, generates an acid (strong acid) in the composition that can dissociate an acid-dissociable group from a component in the radiation-sensitive composition.
• the term "acid diffusion controller” refers to a component that can inhibit the diffusion of an acid derived from the acid generator generated by exposure in the resist film, thereby inhibiting a chemical reaction caused by the acid in the non-exposed region.
• the onium salt compounds are classified as acid generators or acid diffusion controllers depending on the relative acid strength.
• the degree of acidity can be evaluated by the acid dissociation constant (pKa).
• the acid dissociation constant of the acid that generates the photodegradable base is usually -3 or more, preferably -1 ⁇ pKa ⁇ 7, and more preferably 0 ⁇ pKa ⁇ 5.
• a radiation-sensitive acid generator having an iodine group on one or both of the cation and the organic anion may be referred to as "(B1) acid generator", and an acid diffusion controller having an iodine group on one or both of the cation and the organic anion may be referred to as "(B2) photodegradable base”.
• the present composition preferably contains an acid generator and a photodegradable base as a radiation-sensitive acid generator. At least one of the acid generator and the photodegradable base contained in the present composition may contain compound (B). Specific embodiments of the radiation-sensitive acid generator contained in the present composition include the following embodiments 1 to 3. [Embodiment 1] An embodiment containing an acid generator (B1) and an onium salt compound (hereinafter also referred to as "another photodegradable base”) that generates an acid having a weaker acidity than the acid generated by the acid generator (B1) and is different from the compound (B).
• An embodiment further comprising (B2) a photodegradable base, and an onium salt compound (hereinafter also referred to as "another acid generator") that generates an acid having a stronger acidity than the acid generated by the (B2) photodegradable base and is different from the (B) compound.
• an embodiment including, as the compound (B), an acid generator (B1) which is a first onium salt compound, and a photodegradable base (B2) which is a second onium salt compound that generates an acid having a weaker acidity than the acid generated by the first onium salt compound. Any of these methods can provide a resist film that exhibits excellent LWR performance and reduces the occurrence of development defects while increasing the sensitivity of the radiation-sensitive composition.
• the (B) compound may be an onium salt in which the cation has an iodine group and the organic anion does not have an iodine group, or an onium salt in which the organic anion has an iodine group and the cation does not have an iodine group.
• the (B) compound may also be an onium salt in which both the cation and the organic anion have an iodine group.
• the (B) compound may contain one type alone, or may contain two or more types in combination.
• the number of iodine groups possessed by compound (B) may be one or more. From the viewpoint of achieving both high sensitivity of the composition and improved LWR performance in the resulting resist film, the total number of iodine groups possessed by compound (B) is more preferably two or more. In addition, the number of iodine groups possessed by compound (B) is preferably 10 or less, more preferably 8 or less, taking into consideration the balance between sensitivity and LWR performance, and ease of synthesis.
• the bonding position of the iodine group in the (B) compound is not particularly limited. In terms of being able to obtain a radiation-sensitive composition with higher sensitivity, it is preferable that the (B) compound has a structure in which the iodine group is bonded to an aromatic ring.
• each of the plurality of iodine groups may be bonded to the same aromatic ring in the (B) compound, or may be bonded to different aromatic rings.
• the aromatic ring to which the iodine group is bonded is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.
• the compound (B) is preferably a compound that generates a sulfonic acid, a carboxylic acid, or a sulfonamide in the composition upon exposure to light, and more preferably a compound that generates a sulfonic acid or a carboxylic acid in the composition.
• the compound (B) is preferably an onium salt represented by the following formula (2) or formula (3).
• Y1 and Y2 are monovalent organic groups having 1 to 40 carbon atoms.
• X + is a monovalent onium cation. However, Y1 , X + , or both of them in formula (2) have an iodine group, and Y2 , X + , or both of them in formula (3) have an iodine group.
• the monovalent organic group having 1 to 40 carbon atoms represented by Y1 or Y2 may be a group having a chain structure (hereinafter also referred to as a "chain organic group") or a group having a cyclic structure.
• the chain organic group examples include linear or branched saturated hydrocarbon groups having 1 to 40 carbon atoms, linear or branched unsaturated hydrocarbon groups having 1 to 40 carbon atoms, monovalent groups having 2 to 40 carbon atoms having a (thio)ether group or an ester group between the carbon-carbon bonds of the linear or branched hydrocarbon group, and monovalent groups having 1 to 40 carbon atoms in which any hydrogen atom in the monovalent group or linear or branched hydrocarbon group has been substituted.
• the substituent include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.), hydroxyl groups, and nitro groups.
• examples of the cyclic structure of Y1 or Y2 include an alicyclic hydrocarbon structure having 3 to 20 carbon atoms, an aliphatic heterocyclic structure having 3 to 20 carbon atoms, and an aromatic ring structure having 6 to 20 carbon atoms.
• These cyclic structures may have a substituent.
• the substituent include an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a hydroxyl group, and an oxo group.
• Examples of alicyclic hydrocarbon structures having 3 to 20 carbon atoms include alicyclic monocyclic hydrocarbon structures having 3 to 20 carbon atoms and alicyclic polycyclic hydrocarbon structures having 6 to 20 carbon atoms.
• the alicyclic monocyclic hydrocarbon structures having 3 to 20 carbon atoms and the alicyclic polycyclic hydrocarbon structures having 6 to 20 carbon atoms may be either saturated or unsaturated.
• the alicyclic polycyclic structures may be any of bridged structures, condensed ring structures, and spiro ring structures.
• Examples of the rings contained in the alicyclic monocyclic hydrocarbon structure include cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, etc.
• the alicyclic polycyclic hydrocarbon structure is preferably a bridged alicyclic saturated hydrocarbon structure or a condensed alicyclic saturated hydrocarbon structure, such as a bicyclo[2.2.1]heptane structure, a bicyclo[2.2.2]octane structure, a tricyclo[3.3.1.1 3,7 ]decane structure, a steroid structure, etc.
• Examples of the aliphatic heterocyclic structure having 3 to 20 carbon atoms include a cyclic ether structure, a lactone structure, a cyclic acetal structure, a cyclic carbonate structure, and a sultone structure.
• the aliphatic heterocyclic structure may be either a monocyclic structure or a polycyclic structure.
• the polycyclic structure may be either a bridged structure, a condensed ring structure, or a spiro ring structure.
• the aliphatic heterocyclic structure having 3 to 20 carbon atoms represented by Y1 or Y2 may be a combination of two or more of a bridged structure, a condensed ring structure, and a spiro ring structure.
• the two or more rings constituting the spiro ring structure may be only aliphatic heterocyclic rings, or may be a combination of an aliphatic heterocyclic ring and an alicyclic hydrocarbon ring.
• Aromatic ring structures with 6 to 20 carbon atoms include benzene rings, naphthalene rings, anthracene rings, indene rings, and fluorene rings.
• Y1 or Y2 When Y1 or Y2 is a monovalent group having a cyclic structure, Y1 or Y2 may have a chain structure together with the cyclic structure.
• Y1 or Y2 is a group having a chain structure and a cyclic structure include groups in which the above-mentioned cyclic structure is bonded to a divalent group obtained by removing one hydrogen atom from the above-mentioned monovalent chain organic group.
• Y1 in the above formula (2) and Y2 in the above formula (3) are preferably monovalent groups having a cyclic structure. Furthermore, when Y1 or Y2 has an iodine group, from the viewpoint of increasing the sensitivity of the present composition, it is preferable that the monovalent organic group represented by Y1 or Y2 has an aromatic ring structure.
• Y1 or Y2 does not have an iodine group, it is preferable that it has an alicyclic hydrocarbon structure or an aliphatic heterocyclic structure, and more preferably has a bridged alicyclic saturated hydrocarbon structure or a bridged aliphatic heterocyclic structure, from the viewpoint of increasing the transparency of the film.
• the organic anion when the organic anion has an iodine group, at least one selected from the group consisting of onium salts represented by the following formula (2A) and onium salts represented by the following formula (3A) can be preferably used as the compound (B).
• the onium salt represented by the following formula (2A) can be preferably used as an acid generator.
• the onium salt represented by the following formula (3A) can be preferably used as a photodegradable base.
• W 1 is a monovalent aromatic ring group having 5 to 40 carbon atoms and an iodine group.
• L 1 is a single bond or an (n1+1)-valent organic group.
• n1 is an integer of 1 or more.
• R f1 is a (n1+1)-valent fluorinated hydrocarbon group when L 1 is a single bond, and is a divalent fluorinated hydrocarbon group when L 1 is an (n1+1)-valent organic group.
• X + is a monovalent onium cation.
• W2 is a monovalent aromatic ring group having 5 to 40 carbon atoms and having an iodine group.
• n2 is an integer of 1 or more.
• Rc1 is a single bond or a divalent organic group when n2 is 1, and is an (n2+1)-valent organic group when n2 is 2 or more.
• X + is a monovalent onium cation.
• the monovalent aromatic ring group represented by W 1 or W 2 is preferably a group in which one hydrogen atom is removed from the ring portion of an aromatic ring having a substituent.
• the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, an indene ring, and a fluorene ring, among which a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred.
• the substituent substituting the hydrogen of the aromatic ring includes an iodine group.
• the aromatic ring in W 1 or W 2 may further have a substituent other than an iodine group together with the iodine group.
• substituents include a fluoro group, a bromo group, a chloro group, and a hydroxyl group.
• W 1 and W 2 do not have a fluorine atom.
• the divalent fluorinated hydrocarbon group represented by R f1 is preferably a linear or branched fluorinated saturated hydrocarbon group.
• the fluorinated saturated hydrocarbon group preferably has a structure in which any hydrogen atom in a linear alkanediyl group (preferably having 1 to 5 carbon atoms, more preferably having 1 to 3 carbon atoms) is substituted with a fluoro group or a fluoroalkyl group.
• fluoroalkyl group examples include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, and a 5,5,5-trifluoro-1,1-diethylpentyl group.
• a fluoroalkyl group having 1 to 3 carbon atoms is preferred, and a trifluoromethyl group is more preferred.
• the divalent fluorinated hydrocarbon group represented by R f1 preferably has a fluorine atom or a trifluoroalkyl group bonded to the carbon atom to which the sulfonate anion (—SO 3 ⁇ ) is bonded, and more preferably has a fluorine atom or a trifluoromethyl group bonded to the carbon atom to which the sulfonate anion (—SO 3 ⁇ ) is bonded.
• R f1 is a (n1+1)-valent fluorinated hydrocarbon group
• examples of the group include the above-mentioned divalent fluorinated hydrocarbon groups in which (n1-1) hydrogen atoms have been removed.
• n1 is preferably 1 to 5, more preferably 1 to 3, and further preferably 1 or 2.
• the divalent linking group represented by L1 is preferably -O-, -CO-, -COO-, -OCO-, -O-CO-O-, -S-, -SO 2 -, -CONH-, -NHCO-, or a divalent group in which any methylene group in an alkanediyl group having 2 to 10 carbon atoms is replaced with -O-, -CO-, -COO-, -OCO-, -O-CO-O-, -S-, -SO 2 -, -CONH- or -NHCO-.
• Examples of the divalent organic group represented by R c1 include a substituted or unsubstituted alkanediyl group having 1 to 20 carbon atoms, and a divalent group in which any methylene group in the alkanediyl group is replaced with -O-, -CO-, -COO-, -OCO-, -O-CO-O-, -S-, -SO 2 -, -CONH- or -NHCO-.
• Examples of the substituent include a fluorine atom and a hydroxyl group.
• the number of carbon atoms in the divalent organic group represented by R c1 is preferably 1 to 10.
• R c1 is an (n2+1)-valent organic group
• examples of the organic group include the above-mentioned divalent organic groups from which (n2-1) hydrogen atoms have been removed.
• n2 is preferably 1 to 5, more preferably 1 to 3, and further preferably 1 or 2.
• the cation of the compound (B) preferably has a sulfonium cation structure or an iodonium cation structure from the viewpoint of increasing the sensitivity of the composition and forming a resist film with higher LWR performance.
• X + in the above formula (2) or formula (3) The same applies to X + in the above formula (2) or formula (3).
• the cation of the compound (B) and X + in the above formula (2) or formula (3) preferably have an aromatic ring bonded to a sulfonium cation or an iodonium cation, and at least one group selected from the group consisting of a fluoroalkyl group, a fluoro group (excluding the fluoro group in the fluoroalkyl group) and an iodine group is bonded to the aromatic ring.
• the cation contained in the compound (B) preferably has a triarylsulfonium cation structure or a diaryliodonium cation structure.
• the cation is preferably a cation represented by the following formula (2B) or a cation represented by the following formula (3B).
• R 1a , R 2a , and R 3a are each independently an iodo group, a fluoro group, or a fluoroalkyl group.
• R 4a and R 5a are each independently a monovalent substituent, or R 4a and R 5a taken together represent a single bond or a divalent group connecting the rings to which they are bonded.
• R 6a is a monovalent substituent.
• a1, a2, and a3 are each independently an integer of 0 to 5.
• a4, a5, and a6 are each independently an integer of 0 to 3.
• r is 0 or 1, with the proviso that a1 + a4 ⁇ 5, a2 + a5 ⁇ 5, and a3 + a6 ⁇ 2 ⁇ r + 5 are satisfied.
• R 7a and R 8a are each independently an iodo group, a fluoro group, or a fluoroalkyl group.
• R 9a and R 10a are each independently a monovalent substituent.
• a7 and a8 are each independently an integer of 0 to 5.
• a9 and a10 are each independently an integer of 0 to 3, provided that a7 + a9 ⁇ 5 and a8 + a10 ⁇ 5 are satisfied.
• fluoroalkyl group represented by R 1a , R 2a , R 3a , R 7a and R 8a include the same groups as those described in the description of the fluoroalkyl group contained in the divalent fluorinated hydrocarbon group represented by R f1 in the above formula (2A).
• R 1a , R 2a , R 3a , R 7a and R 8a are preferably an iodo group, a fluoro group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group or a perfluoroethyl group, more preferably an iodo group, a fluoro group or a trifluoromethyl group, and particularly preferably an iodo group or a fluoro group.
• a1, a2 and a3 satisfy "a1 + a2 + a3 ⁇ 1"
• a7 and a8 satisfy "a7 + a8 ⁇ 1".
• an onium salt having a structure in which an iodo group, a fluoro group or a trifluoroalkyl group is directly bonded to an aromatic ring in a triarylsulfonium cation structure or a diaryliodonium cation structure By using an onium salt having a structure in which an iodo group, a fluoro group or a trifluoroalkyl group is directly bonded to an aromatic ring in a triarylsulfonium cation structure or a diaryliodonium cation structure, the sensitivity of the composition can be further improved, and a composition having excellent LWR performance can be obtained.
• 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, a substituted or unsubstituted alkyl group (excluding a fluoroalkyl group), a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkyloxy group, an ester group, an alkylsulfonyl group, a cycloalkylsulfonyl group, a hydroxyl group, a carboxy group, a cyano group, and a nitro group.
• the organic anion constituting the compound (B) may not have an iodine group.
• the structure of the organic anion is not particularly limited.
• the cation constituting the compound (B) has an iodine group and the organic anion does not have an iodine group, the following are specific examples of the organic anion.
• onium salt suitable for use as the acid generator (B1) include compounds represented by the following structural formulas: Note that the compound (B) and the acid generator (B1) are not limited to these examples.
• onium salts suitable for use as the photodegradable base (B2) include compounds represented by the following structural formulas: Note that the compound (B) and the photodegradable base (B2) are not limited to these examples.
• the content of the (B) compound in the composition is preferably 0.5 parts by mass or more, more preferably 2 parts by mass or more, and even more preferably 5 parts by mass or more, per 100 parts by mass of the base resin contained in the composition.
• the content of the (B) compound is preferably 65 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 40 parts by mass or less, per 100 parts by mass of the base resin.
• the content of the acid generator (B1) in the composition is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the base resin contained in the composition.
• the content of the acid generator (B1) is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, relative to 100 parts by mass of the base resin.
• the content of the photodegradable base (B2) in the composition is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, relative to 100 parts by mass of the base resin contained in the composition.
• the content of the photodegradable base (B2) is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, relative to 100 parts by mass of the base resin.
• the present composition containing the polymer (A) and the compound (B) can improve the LWR performance while increasing the sensitivity of the radiation-sensitive composition and further suppress the occurrence of development defects is unclear, but it is thought that, for example, the following is possible.
• a radiation-sensitive acid generator having an iodine group has a high sensitivity to radiation, but tends to be highly hydrophobic due to the presence of iodine atoms. Therefore, when a radiation-sensitive acid generator having an iodine group (i.e., compound (B)) is used, it is expected that high sensitivity can be expected, but solubility in a developer is reduced, and development defects are likely to occur.
• the solubility of the radiation-sensitive composition in a developer is increased by including a polymer (polymer (A)) containing a structural unit represented by the above formula (1) in the radiation-sensitive composition, and thus it is possible to achieve excellent LWR performance and reduced development defects while increasing the sensitivity of the radiation-sensitive composition.
• the present composition may further contain a component other than the polymer (A) and the compound (B).
• a component other than the polymer (A) and the compound (B) examples include a polymer not containing a structural unit represented by the above formula (1) (hereinafter also referred to as “other polymer”), a radiation-sensitive acid generator other than the acid generator (B1) (hereinafter also referred to as “other acid generator”), an acid diffusion controller other than the photodegradable base (B2) (hereinafter also referred to as “other acid diffusion controller”), a solvent, etc.
• the composition preferably contains a base resin as a component other than the (A) polymer.
• the base resin as the other polymer is a polymer different from the (A) polymer and has a lower mass content of fluorine atoms than the (A) polymer.
• the base resin as the other polymer is preferably a polymer (hereinafter also referred to as "(C) polymer") containing a structural unit (third structural unit) containing an acid dissociable group.
• Specific examples and preferred examples of the third structural unit contained in the (C) polymer include the same structural units as those explained as the third structural unit that the (A) polymer may have.
• the content ratio of the third structural unit in the (C) polymer is preferably higher than the content ratio of the third structural unit in the (A) polymer, from the viewpoint of being able to sufficiently increase the difference in solubility in the developer between the exposed and unexposed parts, obtaining a resist film with excellent LWR performance, and sufficiently reducing the occurrence of development defects.
• the content ratio of the third structural unit in the (C) polymer is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total structural units constituting the (C) polymer.
• the content ratio of the third structural unit is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less, based on the total structural units constituting the (C) polymer.
• the (C) polymer may contain only one type of third structural unit, or may contain two or more types.
• the polymer (C) may further contain, in addition to the third structural unit, a structural unit different from the third structural unit and the first structural unit.
• Such structural units include those exemplified as other structural units that the polymer (A) may contain (such as the second structural unit, the fourth structural unit, the fifth structural unit, etc.).
• the (C) polymer when the present composition is used for pattern formation using exposure to radiation having a wavelength of 50 nm or less, such as electron beams or EUV, it is preferable that the (C) polymer further contains the above-mentioned fourth structural unit.
• the content ratio of the fourth structural unit in the (C) polymer is preferably 10 mol % or more, more preferably 15 mol % or more, and even more preferably 20 mol % or more, based on all structural units constituting the (C) polymer.
• the content ratio of the fourth structural unit is preferably 80 mol % or less, more preferably 75 mol % or less, based on all structural units constituting the (C) polymer.
• the (C) polymer may contain only one type of the fourth structural unit, or may contain two or more types.
• the composition may further contain a high fluorine content polymer as another polymer.
• the high fluorine content polymer as the other polymer include the polymer containing the second structural unit exemplified in the explanation of the polymer (A).
• the high fluorine content polymer as the other polymer may further contain, in addition to the second structural unit, one or more of the third to fifth structural units, a structural unit having a non-acid dissociable hydrocarbon group, etc.
• an onium salt composed of a cation and an organic anion and having no iodine group can be preferably used.
• Specific examples of the other acid generator include onium salts composed of an organic anion having no iodine group and a cation having no iodine group, which are exemplified in the description of the compound (B).
• a polymer containing a structural unit having a partial structure that generates an acid in the composition upon exposure to light for example, a structural unit containing a partial structure consisting of a triarylsulfonium cation and an organic anion, or a structural unit containing a partial structure consisting of a diaryliodonium cation and an organic anion
• a polymer containing a structural unit having a partial structure that generates an acid in the composition upon exposure to light for example, a structural unit containing a partial structure consisting of a triarylsulfonium cation and an organic anion, or a structural unit containing a partial structure consisting of a diaryliodonium cation and an organic anion
• the content of the other acid generator in the composition is preferably such that the total content of the acid generator (B1) and the other acid generator is 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more, per 100 parts by mass of the base resin contained in the composition.
• the content of the other acid generator is preferably such that the total content of the acid generator (B1) and the other acid generator is 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, per 100 parts by mass of the base resin.
• One type of the other acid generator may be used alone, or two or more types may be used in combination.
• an onium salt composed of a cation and an organic anion and not having an iodine group can be preferably used.
• the onium salt include the onium salts composed of an organic anion not having an iodine group and a cation not having an iodine group, which are exemplified in the description of the compound (B).
• acid diffusion control agents may also be used, such as compounds other than photodegradable bases (e.g., amino group-containing compounds (alkylamines, aromatic amines, polyamines, etc.), amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and nitrogen-containing compounds having an acid-dissociable group).
• photodegradable bases e.g., amino group-containing compounds (alkylamines, aromatic amines, polyamines, etc.), amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and nitrogen-containing compounds having an acid-dissociable group).
• the content ratio of the other acid diffusion control agent in the composition is preferably such that the total content of the acid diffusion control agent (B2) and the other acid diffusion control agent is 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, relative to 100 parts by mass of the base resin contained in the composition.
• the content ratio of the other acid diffusion control agent is preferably such that the total content ratio of the acid diffusion control agent (B2) and the other acid diffusion control agent is 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, relative to 100 parts by mass of the base resin.
• the other acid diffusion control agent may be used alone or in combination of two or more types.
• the content of the acid diffusion controller is preferably 1 mol % or more, more preferably 2 mol % or more, and even more preferably 5 mol % or more, based on the amount of acid generators contained in the present composition (the total amount when two or more types are used). Furthermore, the content of the acid diffusion controller is preferably 50 mol % or less, more preferably 40 mol % or less, based on the amount of acid generators contained in the present composition. By setting the content of the acid diffusion controller within the above range, the LWR performance of the present composition can be further improved.
• the solvent is not particularly limited as long as it is capable of dissolving or dispersing the components to be blended in the composition, and examples of the solvent include alcohols, ethers, ketones, amides, esters, and hydrocarbons.
• alcohols examples 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; polyhydric alcohols having 2 to 18 carbon atoms, such as 1,2-propylene glycol; and partial ethers of polyhydric alcohols having 3 to 19 carbon atoms, such as propylene glycol monomethyl ether.
• ethers examples 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; and aromatic ring-containing ethers, such as diphenyl ether and anisole.
• 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
• aromatic ring-containing ethers such as diphenyl ether and anisole.
• Ketones include, for example, chain ketones such as 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, di-iso-butyl ketone, and trimethylnonanone; cyclic ketones such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, and methylcyclohexanone; 2,4-pentanedione, acetonylacetone, acetophenone, and diacetone alcohol.
• chain ketones such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, dieth
• Amids include, for example, cyclic amides such as N,N'-dimethylimidazolidinone and N-methylpyrrolidone; chain amides such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpropionamide.
• cyclic amides such as N,N'-dimethylimidazolidinone and N-methylpyrrolidone
• chain amides such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpropionamide.
• Esters include, for example, 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; polycarboxylic acid diesters such as diethyl oxalate; carbonates such as dimethyl carbonate and diethyl carbonate; and cyclic esters such as ⁇ -butyrolactone.
• 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
• polycarboxylic acid diesters such as diethyl oxalate
• carbonates such as dimethyl carbonate and diethyl carbonate
• Hydrocarbons include, for example, aliphatic hydrocarbons with 5 to 12 carbon atoms such as n-pentane and n-hexane; and aromatic hydrocarbons with 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, more preferably contains at least one selected from the group consisting of polyhydric alcohol partial ether carboxylates and cyclic ketones, and even more preferably contains at least one of propylene glycol monomethyl ether acetate (propylene glycol monomethyl ether acetate), ethyl lactate, and cyclohexanone.
• One or more types of solvents can be used.
• the present composition may further contain components other than the above-mentioned (A) polymer, (B) compound, (C) polymer, other acid generators, other acid diffusion controllers, and solvents (hereinafter also referred to as "other optional components").
• other optional components include surfactants, alicyclic skeleton-containing compounds (e.g., 1-adamantanecarboxylic acid, 2-adamantanone, t-butyl deoxycholate, etc.), sensitizers, uneven distribution promoters, etc.
• the content ratio of the other optional components in the present composition can be appropriately selected depending on each component within a range that does not impair the effects of the present disclosure.
• the composition can be produced, for example, by mixing the (A) polymer and (B) compound, as well as the (C) polymer and solvent, etc., in a desired ratio, and filtering the resulting mixture, preferably using a filter (e.g., a filter with a pore size of about 0.2 ⁇ m).
• the solid content concentration of the composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.
• the solid content concentration of the composition is preferably 50% by mass or less, more preferably 20% by mass or less, and even more preferably 5% by mass or less.
• composition thus obtained can be used as a positive pattern-forming composition in which a pattern is formed using an alkaline developer, or as a negative pattern-forming composition in which a developer containing an organic solvent is used.
• the method for forming a resist pattern in the present disclosure includes a step of applying the present composition to one side of a substrate (hereinafter also referred to as a "coating step"), a step of exposing the resist film obtained by the coating step (hereinafter also referred to as an "exposure step”), and a step of developing the exposed resist film (hereinafter also referred to as a "development step”).
• Examples of patterns formed by the method for forming a resist pattern in the present disclosure include a line and space pattern and a hole pattern.
• the resist film is formed using the present composition, so that a resist pattern having good sensitivity and lithography properties and few development defects can be formed. Each step will be described below.
• the composition is coated on one side of the substrate to form a resist film on the substrate.
• substrates can be used as the substrate on which the resist film is formed, and examples of such substrates include silicon wafers, silicon dioxide wafers, and aluminum-coated wafers.
• an organic or inorganic anti-reflective film (see, for example, JP-B-6-12452) may be formed on the substrate before use.
• coating methods for the composition include rotary coating (spin coating), casting coating, and roll coating.
• pre-baking also called PB or soft bake (SB)
• SB soft bake
• the PB temperature is preferably 60 to 140° C., and more preferably 80 to 130° C.
• the PB time is preferably 5 to 600 seconds, and more preferably 10 to 300 seconds.
• the average thickness of the resist film formed is preferably 10 to 1,000 nm, and more preferably 20 to 500 nm.
• the resist film obtained by the coating step is exposed.
• This exposure is performed by irradiating the resist film with radiation through a photomask, or in some cases through an immersion medium such as water.
• radiation include electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and gamma rays; and charged particle beams such as electron beams and alpha rays, depending on the line width of the desired pattern.
• the radiation irradiated to the resist film formed using the present composition is preferably far ultraviolet light, EUV, or electron beam, more preferably ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), EUV, or electron beam, and even more preferably ArF excimer laser light, EUV, or electron beam.
• PEB post-exposure bake
• This PEB can increase the difference in solubility in the developer between the exposed and unexposed areas.
• the PEB temperature is preferably 50 to 180°C, more preferably 80 to 130°C.
• the PEB time is preferably 5 to 600 seconds, more preferably 10 to 300 seconds.
• the exposed resist film is developed with a developer.
• a developer either an alkaline developer or an organic solvent developer may be used, and can be appropriately selected depending on the desired pattern (positive pattern or negative pattern).
• the developer used in the alkaline development may be, for example, an alkaline aqueous solution in which at least one of the following alkaline compounds is dissolved: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene, etc.
• TMAH tetramethylammonium hydroxide
• organic solvent development examples of the organic solvent include organic solvents such as hydrocarbons, ethers, esters, ketones, and alcohols, or solvents containing such organic solvents.
• organic solvent examples include one or more of the solvents listed as solvents that may be blended in the present composition. There are no particular limitations on the development method, and a known method may be appropriately selected and used.
• composition described above contains the polymer (A) and the compound (B), and therefore has good sensitivity to exposure light, is excellent in LWR performance, and can form a resist pattern with few development defects. Therefore, these compositions can be suitably used for forming fine resist patterns in the lithography process of various electronic devices such as semiconductor devices and liquid crystal devices.
• [Means 1] A radiation-sensitive composition comprising: (A) a polymer containing a structural unit represented by the above formula (1); and (B) an onium salt compound comprising an organic anion and a cation, wherein the organic anion, the cation, or both of them have an iodine group, and which generates an acid upon exposure to radiation.
• [Measure 2] The radiation-sensitive composition according to [Measure 1], wherein the compound (B) is represented by the above formula (2) or (3).
• [Measure 3] The radiation-sensitive composition according to [Measure 1] or [Measure 2], wherein the compound (B) has a structure in which an iodine group is bonded to an aromatic ring.
• [Measure 4] The radiation-sensitive composition according to any one of [Measure 1] to [Measure 3], which contains a compound represented by the above formula (2A) as the compound (B).
• [Measure 5] The radiation-sensitive composition according to any one of [Measure 1] to [Measure 4], which contains a compound represented by the above formula (3A) as the compound (B).
• [Measures 6] The radiation-sensitive composition according to any one of [Measures 1] to [Measures 5], further comprising an onium salt compound which generates an acid having a weaker acidity than the acid generated by the compound (B) and which is different from the compound (B).
• [Measures 7] The radiation-sensitive composition according to any one of [Measures 1] to [Measures 6], further comprising an onium salt compound which generates an acid having a stronger acidity than the acid generated by the compound (B) and which is different from the compound (B).
• [Measures 8] The radiation-sensitive composition according to any one of [Measures 1] to [Measures 5], comprising, as the compound (B), a first onium salt compound and a second onium salt compound that generates an acid having a weaker acidity than the acid generated by the first onium salt compound.
• [Measures 9] The radiation-sensitive composition according to any one of [Measures 1] to [Measures 8], wherein the cation has a sulfonium cation structure or an iodonium cation structure.
• [Measure 10] The radiation-sensitive composition according to [Measure 9], wherein the cation has an aromatic ring bonded to a sulfonium cation or an iodonium cation, and at least one group selected from the group consisting of a fluoroalkyl group, a fluoro group (excluding a fluoro group in a fluoroalkyl group), and an iodo group is bonded to the aromatic ring.
• [Measures 11] The radiation-sensitive composition according to any one of [Measures 1] to [Measures 10], wherein the polymer (A) further contains a structural unit having an acid-dissociable group.
• [Measure 12] The radiation-sensitive composition according to any one of [Measure 1] to [Measure 11], wherein the polymer (A) further contains a structural unit having a hydroxyl group bonded to an aromatic ring.
• [Measures 13] The radiation-sensitive composition according to any one of [Measures 1] to [Measures 12], wherein the polymer (A) further contains a structural unit having a fluorine atom.
• [Measures 14] The radiation-sensitive composition according to [Measures 13], wherein the proportion of structural units having fluorine atoms in the polymer (A) is 45 to 99 mol % based on all structural units constituting the polymer (A).
• [Measure 15] The radiation-sensitive composition according to any one of [Measure 1] to [Measure 14], wherein the content of the polymer (A) is 0.1 to 20 mass % based on the total amount of the composition excluding the solvent.
• [Measures 16] The radiation-sensitive composition according to any one of [Measures 1] to [Measures 15], wherein the proportion of the structural unit represented by formula (1) in the polymer (A) is 1 to 55 mol % based on all structural units constituting the polymer (A).
• [Measures 17] The radiation-sensitive composition according to any one of [Measures 1] to [Measures 16], further comprising (C) a polymer which has a structural unit containing an acid-dissociable group and is different from the polymer (A), wherein the polymer (A) has a higher mass content of fluorine atoms than the polymer (C).
• [Means 18] The radiation-sensitive composition according to any one of [Means 1] to [Means 17], wherein E + in the formula (1) is represented by the formula (e-1), formula (e-2) or formula (e-3).
• [Means 19] The radiation-sensitive composition according to any one of [Means 1] to [Means 18], wherein D ⁇ in the above formula (1) is “—COO ⁇ ”, “—SO 3 ⁇ ”, “—PO 3 ⁇ ”, “—POO ⁇ ” or “—O ⁇ ”.
• [Means 20] A method for forming a resist pattern, comprising the steps of applying the radiation-sensitive composition according to any one of [Means 1] to [Means 19] onto a substrate to form a resist film, exposing the resist film to light, and developing the exposed resist film.
• Second structural unit (Monomers that provide other structural units) Second structural unit
• Synthesis of Polymer (A) [Synthesis Example 1] Synthesis of Polymer (A-1) Compound (M-1) and compound (M-12) were dissolved in 2-butanone (200 parts by mass relative to the total monomer amount) so that the molar ratio was 5/95. Azobisisobutyronitrile (AIBN) was added as a polymerization initiator at 6 mol% relative to the total monomers to prepare a monomer solution. Meanwhile, 2-butanone (100 parts by mass) was placed in an empty reaction vessel and heated to 80°C while stirring. Next, the monomer solution prepared above was dropped over 3 hours. Then, it was heated at 80°C for another 3 hours. After the polymerization reaction was completed, the polymerization solution was cooled to room temperature.
• AIBN Azobisisobutyronitrile
• Synthesis of Polymer (C) [Synthesis Example 47] Synthesis of Polymer (C-1) Compound (M-35) and compound (M-23) were dissolved in methanol (200 parts by mass relative to the total monomer amount) so that the molar ratio was 70/30. Next, 6 mol% of AIBN was added as a polymerization initiator relative to the total monomer amount to prepare a monomer solution. Meanwhile, 1-methoxy-2-propanol (100 parts by mass relative to the total monomer amount) was added to an empty reaction vessel and heated to 85°C with stirring. Next, the monomer solution prepared above was dropped over 3 hours, and then heated at 85°C for another 3 hours. After the polymerization reaction was completed, the polymerization solution was cooled to room temperature.
• the cooled polymerization solution was poured into hexane (500 parts by mass relative to the polymerization solution), and the precipitated white powder was filtered off.
• the filtered white powder was washed twice with 100 parts by mass of hexane relative to the polymerization solution, and then redissolved in 1-methoxy-2-propanol (300 parts by mass).
• methanol 500 parts by mass
• triethylamine 50 parts by mass
• ultrapure water 10 parts by mass
• the resin was solidified by dropping into 500 parts by mass of water, and the obtained solid was filtered off. The resulting mixture was dried at 50° C. for 12 hours to synthesize a white powdery polymer (C-1).
• the Mw and Mw/Mn of the obtained polymer are shown in Table 2.
• Bp-1 to Bp-16 Compounds represented by the following formulas (Bp-1) to (Bp-16)
• Bq-1 to Bq-16 Compounds represented by the following formulas (Bq-1) to (Bq-16).
• Example 1 1 part by mass of polymer (A-2), 100 parts by mass of polymer (C-2), 20 parts by mass of acid generator (Bp-1), 20 mol % of acid diffusion controller (Bq-1) relative to acid generator (Bp-1), 4,800 parts by mass of solvent (E-1), and 2,000 parts by mass of solvent (E-2) were blended and mixed. Next, the resulting mixture was filtered through a membrane filter having a pore size of 0.20 ⁇ m to prepare radiation-sensitive composition (R-1).
• PEB post-exposure bake
• the exposure dose required to form a 32 nm line and space pattern was defined as the optimum exposure dose (Eop), and this optimum exposure dose was defined as the sensitivity (mJ/cm 2 ).
• Eop the optimum exposure dose
• sensitivity mJ/cm 2
• the resist film was exposed to an optimal exposure dose and developed to form a 32 nm line and space pattern.
• the number of defects on this wafer was measured using a defect inspection device (KLA-Tencor's "KLA2810").
• the defects on the wafer were classified into those determined to be originating from the resist film and those due to foreign matter originating from the external environment.
• the number of development defects was judged as "A" (very good) when the number of defects determined to be originating from the resist film was less than 40, "B" (good) when the number was 40 to 50, and "C” (bad) when the number was more than 50.
• the radiation-sensitive compositions used in the examples had good sensitivity and LWR performance, and also had a small number of development defects.
• the radiation-sensitive compositions used in the comparative examples were inferior to the examples in at least one of the evaluations of sensitivity, LWR performance, and number of development defects.
• the radiation-sensitive composition and resist pattern forming method described above can form a resist pattern that has good sensitivity to exposure light, excellent LWR performance, and few development defects. Therefore, they can be suitably used for forming fine resist patterns in the lithography process of various electronic devices such as semiconductor devices and liquid crystal devices.

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