Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
  • C09D125/02—Homopolymers or copolymers of hydrocarbons
  • C09D125/04—Homopolymers or copolymers of styrene
  • C09D125/08—Copolymers of styrene
  • C09D125/14—Copolymers of styrene with unsaturated esters
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/094—Multilayer resist systems, e.g. planarising layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
  • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
  • H10P76/2041—Photolithographic processes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
  • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks

Definitions

• the present invention relates to a composition for forming a resist underlayer film, an underlayer film, and a method for manufacturing a semiconductor device.
• a thin film of a photoresist composition is formed on a semiconductor substrate such as a silicon wafer, and then the thin film is irradiated with active light such as ultraviolet light through a mask pattern on which a device pattern is drawn, developed, and the substrate is etched using the resulting photoresist pattern as a protective film, forming fine projections and recesses on the substrate surface that correspond to the photoresist pattern.
• the present invention provides a composition for forming a resist underlayer film that can form a photoresist pattern with high accuracy even when a substrate containing nitrogen atoms is used, and that can be used as an anti-reflective film during exposure. Furthermore, the present invention provides a composition that can suppress the diffusion of amine components derived from the substrate during the period of time that elapses between the formation of a pattern and the formation of a resist underlayer film on a substrate, and the deterioration of the accuracy of the photoresist pattern.
• a composition comprising a polymer and a crosslinking agent,
• the polymer has a structural unit (A) having a polycyclic aromatic structure
• a composition for forming a resist underlayer film which is used in lithography using a photoresist film or an electron beam resist film, for forming an underlayer film of the resist film on a nitrogen atom-containing substrate.
• a composition for forming a resist underlayer film according to [1] wherein the polymer has the polycyclic aromatic structure in a side chain of the polymer.
• the unit structure (C-1) is a unit structure represented by the following formula (C-1-1):
• the unit structure (C-2) is a unit structure represented by the following formula (C-2-1):
• R 21 represents a hydrogen atom or a methyl group.
• X 21 represents a single bond, an ester group or an amide group.
• Y 21 represents a single bond or an alkylene group having 1 to 6 carbon atoms.
• R 22 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom.
• n represents an integer of 0 to 5. When there are two or more R 22 , the two or more R 22 may be the same or different.
• R 23 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or an aryl group having 6 to 10 carbon atoms which may be substituted with a halogen atom.
• the polymer further has a unit structure (B) having a reactive group, and at least one unit structure (C) selected from a unit structure (C-1) having a monocyclic aromatic structure and a unit structure (C-2) derived from a maleimide structure, the crosslinking agent has a functional group capable of reacting with the reactive group
• the unit structure (A) is a unit structure represented by the following formula (A-1):
• the unit structure (B) is at least one of a unit structure represented by the following formula (B-1) and a unit structure represented by the following formula (B-2):
• the unit structure (C-1) is a unit structure represented by the following formula (C-1-1):
• the unit structure (C-2) is a unit structure represented by the following formula (C-2-1): the molar ratio of the unit structure (A) to all unit structures of the polymer is 40 mol % or more,
• R 1 represents a hydrogen atom or a methyl group
• X 1 represents a single bond, an ester group or an amide group
• Y 1 represents a single bond or an alkylene group having 1 to 6 carbon atoms
• Ar represents a monovalent group obtained by removing a hydrogen atom from optionally substituted naphthalene, anthracene, phenanthrene, pyrene, triphenylene, chrysene, naphthacene, biphenylene, fluorene or carbazole.
• R 11 represents a hydrogen atom or a methyl group
• X 11 represents an ester group or an amide group
• R 12 represents a monovalent group having 1 to 6 carbon atoms and the reactive group.
• R 13 represents a monovalent group having 1 to 6 carbon atoms and having the reactive group.
• R 21 represents a hydrogen atom or a methyl group.
• X 21 represents a single bond, an ester group or an amide group.
• Y 21 represents a single bond or an alkylene group having 1 to 6 carbon atoms.
• R 22 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom.
• n represents an integer of 0 to 5. When there are two or more R 22 , the two or more R 22 may be the same or different.
• R 23 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or an aryl group having 6 to 10 carbon atoms which may be substituted with a halogen atom.
• the method for producing a substrate provided with a resist pattern according to [15] further comprising the step of forming the resist film 12 hours or more after the formation of the underlayer film.
• a method for manufacturing a semiconductor device comprising the steps of:
• the present invention it is possible to form a resist underlayer film that can suppress a decrease in resist resolution due to diffusion of amine components. Furthermore, according to the present invention, it is possible to form a resist underlayer film that is resistant to a decrease in resolution even if a predetermined period of time has passed between the formation of the resist underlayer film on the substrate and the formation of the pattern.
• composition for forming resist underlayer film is used in lithography using a photoresist film or an electron beam resist film, for forming an underlayer film of the resist film on a nitrogen atom-containing substrate.
• the composition for forming a resist underlayer film of the present invention contains a polymer and a crosslinking agent.
• the polymer has a unit structure (A) having a polycyclic aromatic structure.
• the composition for forming a resist underlayer film contains a polymer and a crosslinking agent, and the polymer has a unit structure (A) having a polycyclic aromatic structure, so that a resist underlayer film capable of suppressing a decrease in the resolution of the resist can be formed.
• A unit structure having a polycyclic aromatic structure
• the predetermined period is, for example, 12 hours or more, 24 hours or more, 48 hours or more, 72 hours or more, or 92 hours or more.
• the storage temperature is, for example, 20° C. to 30° C.
• the storage humidity is, for example, 30 to 70% RH, 30 to 60% RH, or 35 to 55% RH.
• the polymer has a unit structure (A) having a polycyclic aromatic structure.
• the polymer preferably has the polycyclic aromatic structure in a side chain.
• the polymer preferably has a unit structure (B) having a reactive group.
• the crosslinking agent preferably has a reactive group capable of reacting with the reactive group.
• this polymer may be referred to as a "specific polymer.”
• the unit structure (A) is a unit structure having a polycyclic aromatic structure.
• the polycyclic aromatic structure refers to a structure composed of two or more aromatic rings that exhibit aromaticity, and includes a fused polycyclic aromatic structure having a fused ring, and an aromatic ring assembly structure in which a plurality of aromatic rings are directly bonded to each other via single bonds.
• the polycyclic aromatic structure may be a structure composed only of hydrocarbons, or may be a structure having a heteroatom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom).
• Fused polycyclic aromatic structures include, but are not limited to, naphthalene structures, anthracene structures, phenanthrene structures, pyrene structures, triphenylene structures, chrysene structures, naphthacene structures, biphenylene structures, and fluorene structures.
• Aromatic ring assembly structures are not particularly limited, but examples include a carbazole structure, a biphenyl structure, a terphenyl structure, a quaterphenyl structure, a binaphthalene structure, a phenylnaphthalene structure, a phenylfluorene structure, and a diphenylfluorene structure.
• the polycyclic aromatic structure is preferably selected from optionally substituted naphthalene, anthracene, phenanthrene, pyrene, triphenylene, chrysene, naphthacene, biphenylene, fluorene, and carbazole.
• the polycyclic aromatic structure may be substituted with a substituent.
• the optionally substituted substituent is not particularly limited, and examples thereof include a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, a thiol group, a cyano group, a carboxy group, an amino group, an amide group, an alkoxycarbonyl group, and a thioalkyl group.
• halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the alkyl group include alkyl groups having 1 to 6 carbon atoms.
• alkyl group having 1 to 6 carbon atoms examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl- Examples of such alkyl groups include an n-pentyl group, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-
• a cyclic alkyl group can also be used as the alkyl group.
• cyclic alkyl groups having 1 to 10 carbon atoms include cyclopropyl group, cyclobutyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, cyclopentyl group, 1-methylcyclobutyl group, 2-methylcyclobutyl group, 3-methylcyclobutyl group, 1,2-dimethylcyclopropyl group, 2,3-dimethylcyclopropyl group, 1-ethylcyclopropyl group, 2-ethylcyclopropyl group, cyclohexyl group, 1-methylcyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 1-ethylcyclobutyl group, 2-ethylcyclobutyl group, 3-ethylcyclobutyl group, 1,2-dimethyl -cyclobutyl group, 1,3-dimethyl-cyclobutyl
• Examples of the alkoxy group include alkoxy groups having 1 to 6 carbon atoms. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, and an isopropoxy group. Examples of the amide group include amide groups having 1 to 12 carbon atoms. Examples of the amide group having 1 to 12 carbon atoms include a formamide group, an acetamide group, a propionamide group, an isobutylamide group, a benzamide group, a naphthylamide group, and an acrylamide group. Examples of the alkoxycarbonyl group include an alkoxycarbonyl group having 2 to 12 carbon atoms.
• Examples of the alkoxycarbonyl group having 2 to 12 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, and a benzyloxycarbonyl group.
• Examples of the thioalkyl group include thioalkyl groups having 1 to 6 carbon atoms. Examples of the thioalkyl group include a methylthio group, an ethylthio group, a butylthio group, and a hexylthio group.
• the polycyclic aromatic structure is preferably a naphthalene structure, an anthracene structure, a phenanthrene structure, a pyrene structure, a triphenylene structure, a chrysene structure, a naphthacene structure, a biphenylene structure, a fluorene structure, or a carbazole structure, more preferably a naphthalene structure, an anthracene structure, a phenanthrene structure, a pyrene structure, or a carbazole structure, and even more preferably a naphthane structure or a carbazole structure.
• the polycyclic aromatic structure may be of one type or two or more types, but is preferably of one or two types.
• the unit structure (A) is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, a unit structure represented by the following formula (A-1) is preferred.
• R 1 represents a hydrogen atom or a methyl group
• X 1 represents a single bond, an ester group or an amide group
• Y 1 represents a single bond or an alkylene group having 1 to 6 carbon atoms
• Ar represents a monovalent group obtained by removing a hydrogen atom from optionally substituted naphthalene, anthracene, phenanthrene, pyrene, triphenylene, chrysene, naphthacene, biphenylene, fluorene or carbazole.
• the unit structure represented by formula (A-1) includes vinylnaphthalene having naphthalene as the side chain as Ar.
• Examples of the substituents that Ar may have include halogen atoms, hydroxy groups, alkyl groups, alkoxy groups, thiol groups, cyano groups, carboxy groups, amino groups, amide groups, alkoxycarbonyl groups, and thioalkyl groups.
• the unit structure represented by formula (A-1) is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, the unit structure represented by the following formula (A-1-1) is preferred.
• R 1 represents a hydrogen atom or a methyl group.
• R 2 represents a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, a thiol group, a cyano group, a carboxy group, an amino group, an amido group, an alkoxycarbonyl group, or a thioalkyl group.
• n represents an integer of 0 to 7.
• the two or more R 2's may be the same or different.
• Examples of the unit structure represented by formula (A-1) include the following.
• the unit structure (A) in a particular polymer may be of one or more types, but is preferably of one or two types.
• the unit structure (B) is a unit structure having a reactive group.
• the unit structure (B) is a structure different from the unit structure (A).
• the unit structure (B) does not have a polycyclic aromatic structure.
• the reactive group possessed by the unit structure (B) is not particularly limited, but examples thereof include a hydroxy group, an epoxy group, an acyl group, an acetyl group, a formyl group, a benzoyl group, a carboxy group, a carbonyl group, an amino group, an imino group, a cyano group, an azo group, an azido group, a thiol group, a sulfo group, and an allyl group.
• the unit structure (B) is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferable that the unit structure (B) is at least one of a unit structure represented by the following formula (B-1) and a unit structure represented by the following formula (B-2).
• R 11 represents a hydrogen atom or a methyl group
• X 11 represents an ester group or an amide group
• R 12 represents a monovalent group having 1 to 12 carbon atoms and a reactive group.
• R 13 represents a monovalent group having 1 to 12 carbon atoms and a reactive group.
• Examples of the monovalent group having 1 to 12 carbon atoms and having a reactive group for R 12 and R 13 include a hydroxyalkyl group having 1 to 12 carbon atoms.
• Examples of the hydroxyalkyl group having 1 to 12 carbon atoms include hydroxyalkyl groups having 1 to 6 carbon atoms.
• hydroxyalkyl groups having 1 to 12 carbon atoms include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, a hydroxycyclohexyl group, a dihydroxycyclohexyl group, and a 3-hydroxy-1-adamantyl group.
• the number of hydroxy groups contained in the hydroxyalkyl group having 1 to 12 carbon atoms may be one or two or more.
• a unit structure represented by formula (B-1) is the unit structure represented by the following formula (B-1-1).
• R 11 and R 12 have the same meanings as R 11 and R 12 in formula (B-1), respectively.
• Examples of the unit structure represented by formula (B-1) include the following.
• Examples of the unit structure represented by formula (B-2) include the following.
• unit structures containing an epoxy group as a reactive group include unit structures derived from compounds represented by general formulas (I) to (XVII) described in JP 2012-62365 A.
• the unit structure (B) in a particular polymer may be of one or more types, but is preferably of one or two types.
• the specific polymer may have a unit structure other than the unit structure (A) and the unit structure (B).
• a unit structure from the viewpoint of suitably obtaining the effects of the present invention, at least any one of the unit structures (C) of the unit structure (C-1) having a monocyclic aromatic structure and the unit structure (C-2) derived from a maleimide structure is preferable.
• the unit structure (C) is a unit structure different from the unit structures (A) and (B).
• the unit structure (C) does not have a polycyclic aromatic structure and the reactive group contained in the unit structure (B).
• the monocyclic aromatic ring contained in the unit structure (C-1) may be an aromatic hydrocarbon ring or an aromatic heterocycle, with an aromatic hydrocarbon ring being preferred.
• An example of such an aromatic hydrocarbon ring is a benzene ring.
• the unit structure (C) is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferable that the unit structure (C-1) is at least one of the unit structure (C-1) represented by the following formula (C-1-1) and the unit structure (C-2) represented by the following formula (C-1-2).
• R 21 represents a hydrogen atom or a methyl group.
• X 21 represents a single bond, an ester group or an amide group.
• Y 21 represents a single bond or an alkylene group having 1 to 6 carbon atoms.
• R 22 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom.
• n represents an integer of 0 to 5.
• R 23 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or an aryl group having 6 to 10 carbon atoms which may be substituted with a halogen atom.
• Examples of the unit structure represented by formula (C-1-1) include a unit structure represented by the following formula (C-1-1-1) and a unit structure represented by the following formula (C-1-1-2).
• R 21 represents a hydrogen atom or a methyl group.
• Y 21 represents a single bond or an alkylene group having 1 to 6 carbon atoms.
• R 22 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom.
• n represents an integer of 0 to 5. When there are two or more R 22 , the two or more R 22 may be the same or different.
• n is preferably an integer from 1 to 5.
• Examples of the unit structure represented by formula (C-1-1) include the following.
• Examples of the unit structure represented by formula (C-1-2) include the following.
• the unit structure (C) in a particular polymer may be one or more types, but preferably one or two types.
• the molar ratio of the unit structure (A) to all unit structures of the specific polymer is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 40 mol % or more, more preferably 45 mol % or more, and particularly preferably 50 mol % or more.
• the molar ratio of the unit structure (A) to all unit structures of the specific polymer is preferably 95 mol % or less, more preferably 90 mol % or less, and particularly preferably 80 mol % or less.
• the molar ratio of the unit structure (B) to all unit structures of the specific polymer is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 5 mol % or more, more preferably 10 mol % or more, and particularly preferably 15 mol % or more.
• the molar ratio of the unit structure (B) to all unit structures of the specific polymer is preferably 40 mol % or less, more preferably 35 mol % or less, and particularly preferably 30 mol % or less.
• the molar ratio of the unit structure (C) to all unit structures of the specific polymer is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, it is preferably 5 mol % or more, more preferably 10 mol % or more, and particularly preferably 15 mol % or more.
• the molar ratio of the unit structure (C) to all unit structures of the specific polymer is preferably 40 mol % or less, more preferably 35 mol % or less, and particularly preferably 30 mol % or less.
• the molar ratio of unit structure (A) to unit structure (B) in a specific polymer (unit structure (A)/unit structure (B)) is not particularly limited, but is preferably 1 to 9, and more preferably 1.5 to 5.
• the distribution of unit structures in a particular polymer is not particularly limited.
• the particular polymer may be a block copolymer or a random copolymer.
• the molecular weight of the specific polymer is not particularly limited, but the weight average molecular weight measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC) is preferably 1,500 to 100,000, and more preferably 2,000 to 50,000.
• GPC gel permeation chromatography
• the method for producing the specific polymer is not particularly limited, and for example, the specific polymer of the present embodiment can be obtained by reacting a carbon-carbon double bond contained in a monomer that provides unit structure (A), a carbon-carbon double bond contained in a monomer that provides unit structure (B), and a carbon-carbon double bond contained in a monomer that provides any unit structure (C).
• a known polymerization method such as radical polymerization, anionic polymerization, or cationic polymerization can be used.
• Various known techniques such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization can also be used.
• the polymerization initiator used during polymerization is not particularly limited, but examples thereof include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2 , 2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], and 2,2'-azobis(2-methylpropionamidine)
• the solvent used during polymerization is not particularly limited, but examples include dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-
• the reaction temperature is not particularly limited, but may be, for example, 20°C to 150°C.
• the reaction time is not particularly limited, but may be, for example, 1 hour to 72 hours.
• the obtained solution containing the polymer can be used as is for preparing a composition for forming a resist underlayer film.
• the polymer can also be recovered and used after being precipitated and isolated in a poor solvent such as methanol, ethanol, isopropanol, water, or a mixture thereof.
• the content of the specific polymer in the composition for forming a resist underlayer film is not particularly limited, but from the viewpoint of solubility, it is preferably 0.1% by mass to 50% by mass, and more preferably 0.1% by mass to 10% by mass, based on the entire composition for forming a resist underlayer film.
• the content of the specific polymer in the composition for forming a resist underlayer film is preferably 50% by mass to 95% by mass, more preferably 55% by mass to 90% by mass, and particularly preferably 60% by mass to 85% by mass, based on the film-constituting components.
• the film constituent components refer to the components contained in the composition other than the solvent.
• the composition for forming a resist underlayer film contains a crosslinking agent.
• the crosslinking agent preferably has a functional group capable of reacting with the reactive group in the unit structure (B).
• the number of the functional groups in the crosslinking agent is not particularly limited, and may be one, or two or more.
• the functional group capable of reacting with the reactive group possessed by the unit structure (B) is not particularly limited, and examples thereof include a hydroxy group, an epoxy group, an acyl group, an acetyl group, a formyl group, a benzoyl group, a carboxy group, a carbonyl group, an amino group, an imino group, a cyano group, an azo group, an azido group, a thiol group, a sulfo group, an allyl group, and a structure represented by the following formula (D).
• R 101 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bond.
• the bond is, for example, bonded to a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring.
• a functional group capable of reacting with the reactive group of unit structure (B) is, for example, a structure represented by formula (D).
• examples of functional groups that can react with the reactive group of the unit structure (B) include a carboxy group, an amino group, and a thiol group.
• crosslinking agents examples include compounds having two or more structures represented by the above formula (D).
• R 101 is preferably a hydrogen atom, a methyl group, an ethyl group or a group represented by the following structure.
• R 102 represents a hydrogen atom, a methyl group, or an ethyl group. * represents a bond.
• Preferred crosslinking agents are melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, and compounds having a phenolic hydroxyl group. These can be used alone or in combination of two or more.
• the melamine compound is not particularly limited as long as it has a group capable of reacting with the reactive group (e.g., hydroxy group) of the unit structure (B).
• the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which one to six methylol groups of hexamethylol melamine are methoxymethylated or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, a compound in which one to six methylol groups of hexamethylol melamine are acyloxymethylated or a mixture thereof, and the like.
• the guanamine compound is not particularly limited as long as it has a group capable of reacting with the reactive group (for example, a hydroxyl group) of the unit structure (B).
• the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound in which one to four methylol groups of tetramethylol guanamine are methoxymethylated or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxyguanamine, a compound in which one to four methylol groups of tetramethylol guanamine are acyloxymethylated or a mixture thereof, and the like.
• the glycoluril compound is not particularly limited as long as it has a group capable of reacting with the reactive group (for example, a hydroxyl group) of the unit structure (B).
• glycoluril compounds include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which one to four methylol groups of tetramethylol glycoluril are methoxymethylated or mixtures thereof, and compounds in which one to four methylol groups of tetramethylol glycoluril are acyloxymethylated or mixtures thereof.
• the glycoluril compound may be, for example, a glycoluril derivative represented by the following formula (1E).
• the four R 1s each independently represent a methyl group or an ethyl group
• R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.
• glycoluril derivative represented by formula (1E) examples include compounds represented by the following formulas (1E-1) to (1E-6).
• the glycoluril derivative represented by formula (1E) can be obtained, for example, by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).
• R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represent an alkyl group having 1 to 4 carbon atoms.
• R 1 represents a methyl group or an ethyl group.
• glycoluril derivative represented by formula (2E) examples include compounds represented by the following formulae (2E-1) to (2E-4).
• Examples of the compound represented by formula (3d) include compounds represented by the following formulae (3d-1) and (3d-2).
• the urea compound is not particularly limited as long as it has a group capable of reacting with the reactive group (for example, a hydroxyl group) of the unit structure (B).
• the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethylol urea compounds in which one to four methylol groups are methoxymethylated, or mixtures thereof, and tetramethoxyethyl urea.
• Examples of the compound having a phenolic hydroxy group include compounds represented by the following formula (111) or (112).
• Q2 represents a single bond or an m2-valent organic group.
• R 8 , R 9 , R 11 and R 12 each represent a hydrogen atom or a methyl group.
• R7 and R10 each represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.
• n9 is an integer satisfying 1 ⁇ n9 ⁇ 3, n10 is an integer satisfying 2 ⁇ n10 ⁇ 5, n11 is an integer satisfying 0 ⁇ n11 ⁇ 3, n12 is an integer satisfying 0 ⁇ n12 ⁇ 3, and 3 ⁇ ( n9 + n10 + n11 + n12 ) ⁇ 6.
• n13 is an integer satisfying 1 ⁇ n13 ⁇ 3, n14 is an integer satisfying 1 ⁇ n14 ⁇ 4, n15 is an integer satisfying 0 ⁇ n15 ⁇ 3, n16 is an integer satisfying 0 ⁇ n16 ⁇ 3, and 2 ⁇ ( n13 + n14 + n15 + n16 ) ⁇ 5.
• m2 represents an integer from 2 to 10.
• the m2-valent organic group for Q2 includes, for example, an m2-valent organic group having 1 to 4 carbon atoms.
• Examples of the compound represented by formula (111) or formula (112) include the following compounds.
• the above compound is available as a product of Asahi Yukizai Kogyo Co., Ltd. and Honshu Chemical Industry Co., Ltd.
• An example of the product is TMOM-BP, a product name of Asahi Yukizai Kogyo Co., Ltd.
• glycoluril compounds are preferred, specifically tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, a compound in which one to four methylol groups of tetramethylol glycoluril are methoxymethylated or a mixture thereof, and a compound in which one to four methylol groups of tetramethylol glycoluril are acyloxymethylated or a mixture thereof, with tetramethoxymethyl glycoluril being preferred.
• the molecular weight of the crosslinking agent is not particularly limited, but is preferably 500 or less.
• the content of the crosslinking agent in the composition for forming the resist underlayer film is not particularly limited, but is preferably 5% by mass to 60% by mass of the specific polymer, more preferably 10% by mass to 55% by mass, and particularly preferably 20% by mass to 50% by mass.
• the curing catalyst contained as an optional component in the composition for forming a resist underlayer film may be either a thermal acid generator or a photoacid generator, but it is preferable to use a thermal acid generator.
• thermal acid generators include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate (pyridinium p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonate salt), pyridinium trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-methylmorpholine p-toluenesulfonic acid, N-
• photoacid generators examples include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.
• onium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butanesulfonate, diphenyliodonium perfluoronormal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium triflu
• sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.
• disulfonyldiazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.
• the content of the curing catalyst relative to the crosslinking agent is, for example, 0.1% by mass to 50% by mass, and preferably 1% by mass to 30% by mass.
• a surfactant may be further added to the composition for forming a resist underlayer film in order to prevent pinholes, striations, and the like from occurring and to further improve the coatability against surface unevenness.
• surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, and the like; nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan
• the amount of these surfactants to be added is not particularly limited, but is usually 2.0% by mass or less, and preferably 1.0% by mass or less, based on the composition for forming a resist underlayer film. These surfactants may be added alone or in combination of two or more kinds.
• the composition for forming a resist underlayer film may contain a solvent.
• the solvent is preferably an organic solvent generally used in chemicals for semiconductor lithography processes, specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cyclohexane ...
• Examples of the solvent include heptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, ⁇ -butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used alone or in combination of two or more.
• propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred.
• Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.
• the content of the solvent in the composition for forming the resist underlayer film is not particularly limited, but is preferably 80% by mass to 99.99% by mass, more preferably 90% by mass to 99.95% by mass, and particularly preferably 95% by mass to 99.9% by mass.
• the substrate on which the underlayer film of the resist film is formed using the composition for forming a resist underlayer film of the present invention described above is a nitrogen atom-containing substrate.
• the nitrogen atom-containing substrate may be, for example, a substrate made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, or a substrate having a nitrogen atom-containing film made of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom. Both the substrate and the film on the substrate may contain nitrogen atoms.
• the metal atom is not particularly limited, and examples thereof include titanium, gallium, tungsten, hafnium, zirconium, aluminum, copper, etc.
• the metalloid atom is not particularly limited, and examples thereof include boron, silicon, germanium, arsenic, antimony, tellurium, etc.
• the substrate may be a silicon wafer, a germanium wafer, or a compound semiconductor wafer such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, or aluminum nitride.
• substrates made of a compound having a bond with a nitrogen atom may be gallium nitride, indium nitride, or aluminum nitride.
• examples of the film include polysilicon film, silicon oxide film, silicon nitride film, BPSG (Boro-Phospho Silicate Glass) film, titanium nitride film, titanium nitride oxide film, tungsten film, gallium nitride film, and gallium arsenide film formed by, for example, ALD (atomic layer deposition) method, CVD (chemical vapor deposition) method, reactive sputtering method, ion plating method, vacuum deposition method, and spin coating method (spin-on glass: SOG).
• ALD atomic layer deposition
• CVD chemical vapor deposition
• reactive sputtering method reactive sputtering method
• ion plating method ion plating method
• vacuum deposition method vacuum deposition method
• spin coating method spin-on glass: SOG
• the upper limit of the thickness of the nitrogen-atom-containing film is, for example, 200 nm, 150 nm, or 100 nm.
• the lower limit is 5 nm or 10 nm.
• the underlayer film of the present invention (also referred to as resist underlayer film) is a cured product of the above-mentioned composition for forming a resist underlayer film.
• the resist underlayer film can be produced, for example, by applying the above-mentioned composition for forming a resist underlayer film onto a nitrogen atom-containing substrate and baking the applied composition.
• the composition for forming a resist underlayer film of the present invention is applied onto a nitrogen atom-containing substrate by an appropriate application method such as a spinner or coater.
• the underlayer film is then formed by baking using a heating means such as a hot plate.
• the baking conditions are appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 minutes to 60 minutes.
• the baking temperature is 120°C to 350°C
• the baking time is 0.5 minutes to 30 minutes
• the baking temperature is 150°C to 300°C
• the baking time is 0.8 minutes to 10 minutes.
• the thickness of the underlayer film can be, for example, 0.001 ⁇ m (1 nm) to 10 ⁇ m, 0.002 ⁇ m (2 nm) to 1 ⁇ m, 0.005 ⁇ m (5 nm) to 0.5 ⁇ m (500 nm), 0.001 ⁇ m (1 nm) to 0.05 ⁇ m (50 nm), 0.002 ⁇ m (2 nm) to 0.05 ⁇ m (50 nm), 0.003 ⁇ m (3 nm) to 0.05 ⁇ m (50 nm), 0.004 ⁇ m (4 nm) to 0.05 ⁇ m (50 nm), 0.005 ⁇ m (5 nm) to 0.05 ⁇ m (50 nm), 0.003 ⁇ m (3 nm) to 0.05 ⁇ m (50 nm), m) to 0.03 ⁇ m (30 nm), 0.003 ⁇ m (3 nm) to 0.02 ⁇ m (20 nm), 0.005 ⁇ m (5 nm
• the method for measuring the thickness of the underlayer film is as follows.
• the method for manufacturing a semiconductor device of the present invention includes at least the following steps.
• a step of forming an underlayer film on a nitrogen atom-containing substrate using the composition for forming a resist underlayer film of the present invention includes at least the following steps.
• a resist film is formed on an underlayer film.
• the thickness of the resist film is, for example, 3,000 nm or less, 2,000 nm or less, 1,800 nm or less, 1,500 nm or less, or 1,000 nm or less.
• the lower limit is 100 nm, 80 nm, 50 nm, 30 nm, 20 nm, or 10 nm.
• the resist film formed on the underlayer film by a known method is not particularly limited as long as it responds to light or electron beam (EB) used for irradiation.
• EB electron beam
• a resist that responds to EB is also called a photoresist.
• photoresists include positive photoresists made of novolac resins and 1,2-naphthoquinone diazide sulfonic acid esters, chemically amplified photoresists made of a binder having a group that decomposes with acid to increase the alkaline dissolution rate and a photoacid generator, chemically amplified photoresists made of a low molecular compound that decomposes with acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, chemically amplified photoresists made of a binder having a group that decomposes with acid to increase the alkaline dissolution rate of the photoresist, a low molecular compound that decomposes with acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator, and resists containing metal elements.
• V146G (trade name) manufactured by JSR Corporation, APEX-E (trade name) manufactured by Shipley, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd. may be mentioned.
• resist compositions include the following compositions:
• An actinic ray-sensitive or radiation-sensitive resin composition comprising: resin A having a repeating unit having an acid-decomposable group in which a polar group is protected with a protecting group that is cleaved by the action of an acid; and a compound represented by the following general formula (121).
• m represents an integer of 1 to 6.
• R 1 and R 2 each independently represent a fluorine atom or a perfluoroalkyl group.
• L 1 represents —O—, —S—, —COO—, —SO 2 — or —SO 3 —.
• L2 represents an alkylene group which may have a substituent or a single bond.
• W1 represents a cyclic organic group which may have a substituent.
• M + represents a cation.
• a metal-containing film-forming composition for extreme ultraviolet or electron beam lithography comprising a compound having a metal-oxygen covalent bond and a solvent, the metal element constituting the compound belonging to Periods 3 to 7 of Groups 3 to 15 of the periodic table.
• a radiation-sensitive resin composition comprising a polymer having a first structural unit represented by the following formula (31) and a second structural unit represented by the following formula (32) containing an acid-dissociable group, and an acid generator.
• Ar is a group obtained by removing (n+1) hydrogen atoms from an arene having 6 to 20 carbon atoms.
• R 1 is a hydroxy group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms.
• n is an integer from 0 to 11. When n is 2 or more, multiple R 1s are the same or different.
• R 2 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
• R 3 is a monovalent group having 1 to 20 carbon atoms containing the above-mentioned acid dissociable group.
• Z is a single bond, an oxygen atom, or a sulfur atom.
• R 4 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
• R 2 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom
• X 1 represents a single bond, -CO-O-* or -CO-NR 4 -*
• * represents a bond to -Ar
• R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have one or more groups selected from the group consisting of a hydroxyl group and a carboxyl group.
• resist films examples include:
• a resist film comprising a base resin containing a repeating unit represented by the following formula (a1) and/or a repeating unit represented by the following formula (a2) and a repeating unit that generates an acid bonded to the polymer main chain upon exposure.
• R A is each independently a hydrogen atom or a methyl group.
• R 1 and R 2 are each independently a tertiary alkyl group having 4 to 6 carbon atoms.
• R 3 is each independently a fluorine atom or a methyl group.
• m is an integer of 0 to 4.
• X 1 is a single bond, a phenylene group or a naphthylene group, or a linking group having 1 to 12 carbon atoms containing at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group.
• X 2 is a single bond, an ester bond, or an amide bond.
• resist materials examples include:
• R A is a hydrogen atom or a methyl group.
• X 1 is a single bond or an ester group.
• X 2 is a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, a part of the methylene groups constituting the alkylene group may be substituted with an ether group, an ester group or a lactone ring-containing group, and at least one hydrogen atom contained in X 2 is substituted with a bromine atom.
• X 3 is a single bond, an ether group, an ester group, or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, a part of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group.
• Rf 1 to Rf 4 are each independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, and at least one of them is a fluorine atom or a trifluoromethyl group. 2 may combine to form a carbonyl group.
• R 1 to R 5 are each independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, some or all of the hydrogen atoms of these groups may be substituted with a hydroxy group, a carboxy group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sultone group, a sulfone group, or a sulfonium salt-containing group, and some of the methylene groups constituting these groups may be substituted with an ether group, an ester group, a carbonyl group, a carbonate group
• a resist material comprising a base resin containing a polymer containing a repeating unit represented by the following formula (a):
• R A is a hydrogen atom or a methyl group.
• R 1 is a hydrogen atom or an acid labile group.
• R 2 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine.
• X 1 is a single bond, a phenylene group, or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms which may contain an ester group or a lactone ring.
• X 2 is -O-, -O-CH 2 - or -NH-.
• m is an integer of 1 to 4.
• u is an integer of 0 to 3, with the proviso that m+u is an integer of 1 to 4.
• a resist composition which generates an acid upon exposure and changes its solubility in a developer by the action of the acid
• the composition contains a base component (A) whose solubility in a developer changes under the action of an acid, and a fluorine additive component (F) that is decomposable in an alkaline developer
• the fluorine additive component (F) is a resist composition containing a fluorine resin component (F1) having a structural unit (f1) containing a base dissociable group, and a structural unit (f2) containing a group represented by the following general formula (f2-r-1):
• Rf 21 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a hydroxyalkyl group, or a cyano group.
• n′′ is an integer of 0 to 2. * represents a bond.
• the structural unit (f1) includes a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).
• R is each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
• X is a divalent linking group having no acid dissociable site.
• a aryl is a divalent aromatic cyclic group which may have a substituent.
• X 01 is a single bond or a divalent linking group.
• R 2 is each independently an organic group having a fluorine atom.
• coatings examples include the following:
• a coating comprising a metal oxo-hydroxo network with organic ligands via metal carbon bonds and/or metal carboxylate bonds.
• RzSnO (2-(z/2)-(x/2)) (OH) x , where 0 ⁇ z ⁇ 2 and 0 ⁇ (
• a coating solution comprising an organic solvent and a first organometallic compound having the formula RSnO (3/2-x/2) (OH) x , where 0 ⁇ x ⁇ 3, wherein the solution contains from about 0.0025M to about 1.5M tin, and R is an alkyl or cycloalkyl group having 3 to 31 carbon atoms, the alkyl or cycloalkyl group being bonded to the tin at a secondary or tertiary carbon atom.
• An aqueous inorganic pattern forming precursor solution comprising water, a mixture of metal suboxide cations, polyatomic inorganic anions, and a radiation sensitive ligand comprising a peroxide group.
• Irradiation with light or electron beams is performed, for example, through a mask (reticle) for forming a predetermined pattern.
• a mask for example, i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet) or EB (electron beam) is used.
• the composition for forming a resist underlayer film of the present invention is preferably applied for EB (electron beam) or EUV (extreme ultraviolet: 13.5 nm) irradiation, and more preferably applied for EUV (extreme ultraviolet) exposure.
• the irradiation energy of the electron beam and the exposure dose of light are not particularly limited.
• baking Post Exposure Bake
• the baking temperature is not particularly limited, but is preferably from 60°C to 150°C, more preferably from 70°C to 120°C, and particularly preferably from 75°C to 110°C.
• the baking time is not particularly limited, but is preferably from 1 second to 10 minutes, more preferably from 10 seconds to 5 minutes, and particularly preferably from 30 seconds to 3 minutes.
• an alkaline developer is used.
• the development temperature is, for example, from 5°C to 50°C.
• the development time may be, for example, from 10 seconds to 300 seconds.
• alkaline developer for example, aqueous solutions of alkalis such as inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and cyclic amines such as pyrrole and piperidine can be used.
• alkalis
• an appropriate amount of alcohols such as isopropyl alcohol and a nonionic surfactant can be added to the aqueous solution of the above-mentioned alkalis.
• preferred developers are aqueous solutions of quaternary ammonium salts, more preferably aqueous solutions of tetramethylammonium hydroxide and aqueous solutions of choline.
• surfactants and the like can be added to these developers.
• a method can also be used in which development is performed with an organic solvent such as butyl acetate instead of an alkaline developer to develop the parts of the photoresist where the alkaline dissolution rate is not improved.
• the underlayer film is etched using the formed resist pattern as a mask.
• the etching may be dry etching or wet etching, but is preferably dry etching.
• dry etching method, etc. dry etching method, etc.
• the weight average molecular weights of the polymers shown in the following Synthesis Examples 1 to 6 and Comparative Synthesis Example 1 in this specification are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC).
• GPC gel permeation chromatography
• a GPC device manufactured by Tosoh Corporation was used, and the measurement conditions etc. are as follows.
• Standard sample polystyrene (manufactured by Tosoh Corporation)
• the reaction solution was dropped into isopropyl alcohol, and the precipitate was collected by suction filtration, and then dried under reduced pressure at 60°C to collect polymer 2.
• the weight average molecular weight Mw measured in terms of polystyrene by GPC was 5900.
• the structure present in polymer 2 is shown in the following formula.
• the reaction solution was dropped into methanol, and the precipitate was collected by suction filtration, and then dried under reduced pressure at 60°C to collect polymer 3.
• the weight average molecular weight Mw measured in terms of polystyrene by GPC was 6600.
• the structure present in polymer 3 is shown in the following formula.
• the reaction solution was dropped into isopropyl alcohol, and the precipitate was collected by suction filtration, and then dried under reduced pressure at 60°C to collect polymer 4.
• the weight average molecular weight Mw measured in terms of polystyrene by GPC was 16,300.
• the structure present in polymer 4 is shown in the following formula.
• the reaction solution was dropped into isopropyl alcohol, and the precipitate was collected by suction filtration, and then dried under reduced pressure at 60°C to collect polymer 5.
• the weight average molecular weight Mw measured in terms of polystyrene by GPC was 11900.
• the structure present in polymer 5 is shown in the following formula.
• the reaction solution was dropped into methanol, and the precipitate was collected by suction filtration, and then dried under reduced pressure at 60°C to collect polymer 6.
• the weight average molecular weight Mw measured in terms of polystyrene by GPC was 7300.
• the structure present in polymer 6 is shown in the following formula.
• Comparative Synthesis Example 1 100.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 66.4 g of 5,5-diethylbarbituric acid (manufactured by Tateyama Chemical Industry Co., Ltd.), and 4.1 g of benzyl triethylammonium chloride were added to 682.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After replacing the atmosphere in the reaction vessel with nitrogen, the reaction was carried out at 130° C. for 24 hours to obtain a solution containing Comparative Polymer 1. When GPC analysis was performed, the obtained Comparative Polymer 1 had a weight average molecular weight of 6,800 in terms of standard polystyrene. The structure present in Comparative Polymer 1 is shown in the following formula.
• Underlayer Film-Forming Composition 1 The components were mixed in the proportions shown in Table 1 and filtered using a polyethylene microfilter having a pore size of 0.05 ⁇ m to prepare compositions for forming an underlayer film in Examples 1 to 6 and a composition for forming an underlayer film in Comparative Example 1.
• PL-LI 1,3,4,6-tetrakis(methoxymethyl)glycoluril (structural formula below)
• Underlayer film-coated wafers were prepared using the same method as above, and the underlayer film was produced by storing it in a clean room for 48 hours.
• a photoresist film was formed on the underlayer film of an underlayer film-coated wafer stored in a clean room for 48 hours using the same method, and the line size of the resist pattern was confirmed after exposure and development.
• the above exposure was performed with the optimal irradiation energy for each example.
• the pattern length was measured using a scanning electron microscope (CG4100, manufactured by Hitachi High-Technologies Corporation). The change in pattern size when stored in a clean room for 48 hours (48 hours later) and when exposed continuously (0 hours later) is shown in Table 2.
• the change in pattern size was smaller than that in Comparative Example 1, even when the underlayer film-coated wafer was stored for 48 hours.
• the reason for the small change in pattern size in each Example is that it is possible to block the amine component even when it diffuses from the base substrate having a film such as SiON, SiN, or TiN.
• the composition for forming a resist underlayer film of this embodiment will be a material that can be widely applied in the coating application of nitrogen-containing substrates for diversifying semiconductor manufacturing processes.

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