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
  • 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
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/20—Diluents or solvents
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • 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

Definitions

• the present invention relates to a composition for forming a resist underlayer film, a resist underlayer film, a substrate for semiconductor processing, a method for manufacturing a semiconductor element, and a method for forming a pattern.
• microfabrication has been carried out by lithography using a photoresist composition.
• the above-mentioned microfabrication is performed by forming a thin film of a photoresist composition on a silicon wafer, irradiating active energy rays such as ultraviolet rays through a mask pattern on which a semiconductor device pattern is drawn, and developing the film.
• This is a processing method in which a silicon wafer is etched using a resist pattern as a protective film.
• BARC bottom anti-reflective coating
• the applicant has developed a method for lithography that has a high anti-reflection effect, no intermixing with the resist layer, provides an excellent resist pattern and wide focus depth margin, and has a high dry etching rate compared to resist.
• An antireflection film-forming composition from which an antireflection film can be obtained has been proposed (see Patent Document 1).
• the composition for forming a resist underlayer film is generally an organic solvent-based composition in which a polymer is dissolved in an organic solvent.
• the replacement of organic solvent-based paints with water-based paints is being actively considered due to the environmental impact of volatile organic solvents and the health of workers who handle paints. Since the composition for forming a resist underlayer film is used in a clean room, volatile organic solvents are not easily released into the environment, and workers are not exposed to organic solvents. However, from the viewpoint of waste liquid treatment and the fact that organic solvent-based compositions are flammable and must be handled and transported with care, aqueous compositions are preferred.
• An object of the present invention is to provide a composition for forming a resist underlayer film, a resist underlayer film, a substrate for semiconductor processing, a method for manufacturing a semiconductor element, and a method for forming a pattern using water as a solvent.
• the present inventors conducted intensive studies and found that the above-mentioned problems could be solved, and completed the present invention having the following gist. That is, the present invention includes the following. [1] Contains a first component, a second component, and a solvent, the second component is a water-soluble polymer, The mass ratio of the first component and the second component (first component: second component) is 99:1 to 50:50, The solvent contains water in an amount of 50% by mass or more based on the solvent. A composition for forming a resist underlayer film.
• [2] Contains a first component and a solvent,
• the first component is a compound containing at least one selected from a structure represented by the following formula (1) and a structure represented by the following formula (2),
• the solvent contains water in an amount of 50% by mass or more based on the solvent.
• a composition for forming a resist underlayer film (In formula (1), X 1 represents a group represented by any of the following formulas (1-1) to (1-4). Z 1 and Z 2 each independently represent a single bond or Represents a divalent group represented by the following formula (1-5).
• Q 1 represents a divalent organic group having at least one selected from an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring.
• R 1 to R 5 are each independently an alkyl group having 1 to 10 carbon atoms, which may be interrupted by a hydrogen atom, an oxygen atom, or a sulfur atom. , represents an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group or a phenyl group.
• the phenyl group is at least one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. It may be substituted with a monovalent group.
• R 1 and R 2 may be bonded to each other to form a ring having 3 to 6 carbon atoms.
• R 3 and R 4 may be bonded to each other to form a ring having 3 to 6 carbon atoms. It may form three to six rings.
• Z 3 represents a single bond or a divalent group represented by the following formula (1-5). * represents a bond.
• the first component is a compound containing at least one selected from a structure represented by the following formula (1) and a structure represented by the following formula (2), The composition for forming a resist underlayer film according to [1].
• X 1 represents a group represented by any of the following formulas (1-1) to (1-4).
• Z 1 and Z 2 each independently represent a single bond or Represents a divalent group represented by the following formula (1-5).
• Q 1 represents a divalent organic group having at least one selected from an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring.
• R 1 to R 5 are each independently an alkyl group having 1 to 10 carbon atoms, which may be interrupted by a hydrogen atom, an oxygen atom, or a sulfur atom.
• the phenyl group is at least one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. It may be substituted with a monovalent group.
• R 1 and R 2 may be bonded to each other to form a ring having 3 to 6 carbon atoms.
• R 3 and R 4 may be bonded to each other to form a ring having 3 to 6 carbon atoms. It may form three to six rings.
• Z 3 represents a single bond or a divalent group represented by the following formula (1-5).
• * represents a bond.
• *1 represents a bond bonded to the carbon atom in formula (1).
• *2 represents a bond bonded to the nitrogen atom in formula (1).
• m1 is an integer from 0 to 4
• m2 is 0 or 1
• m3 is 0 or 1
• m4 is an integer from 0 to 2.
• R 21 to R 26 are each independently a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and 2 to 6 carbon atoms.
• n3 represents 0 or 1. When n3 is 0, n11 represents an integer from 0 to 4. When n3 is 1, n11 represents an integer from 0 to 6.
• R21 When R21 is 2 or more, two or more R21 's may be the same or different.
• Z 4 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms.
• n12 and n13 each independently represent an integer of 0 to 4.
• R22 is 2 or more, two or more R22 's may be the same or different.
• R23 When R23 is 2 or more, two or more R23 's may be the same or different.
• n14 represents an integer from 0 to 4.
• R24 When R24 is 2 or more, two or more R24s may be the same or different.
• Z 5 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms.
• n15 and n16 each independently represent an integer of 0 to 4.
• R25 is 2 or more, two or more R25 's may be the same or different.
• R26 is 2 or more, two or more R26 's may be the same or different.
• a semiconductor substrate, The resist underlayer film according to [11], A substrate for semiconductor processing comprising: [13] Forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to [10]; forming a resist film on the resist underlayer film;
• a method for manufacturing a semiconductor device including: [14] Forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film according to any one of [1] to [10]; forming a resist film on the resist underlayer film; irradiating the resist film with light or an electron beam, and then developing the resist film to obtain a resist pattern; etching the resist lower layer film using the resist pattern as a mask;
• a pattern forming method including:
• the present invention it is possible to provide a composition for forming a resist underlayer film, a resist underlayer film, a substrate for semiconductor processing, a method for manufacturing a semiconductor element, and a method for forming a pattern using water as a solvent.
• the amount of organic solvents conventionally used in this field can be reduced, contributing to a reduction in environmental impact.
• FIG. 1 is a SEM photograph of an example of forming a resist pattern.
• composition for forming resist underlayer film contains a first component and water.
• composition for forming a resist underlayer film of the present invention contains a first component, a second component, and water.
• the first component is an organic compound.
• the first component is, for example, a component that may be used in combination with the second component in the composition for forming a resist underlayer film.
• the first component is an organic compound that dissolves in the above solvent in order to be used as a composition for forming a resist underlayer film.
• the molecular weight of the first component is not particularly limited, and the first component may be a low molecular compound or a high molecular compound.
• the first component is preferably a compound containing at least one selected from a structure represented by the following formula (1) and a structure represented by the following formula (2).
• the first component is a compound containing at least one selected from the structure represented by formula (1) and the structure represented by formula (2) below, it can be obtained from a composition for forming a resist underlayer film. It imparts excellent solvent resistance and antireflection performance to the resist underlayer film.
• X 1 represents a group represented by any of the following formulas (1-1) to (1-4).
• Z 1 and Z 2 each independently represent a single bond or Represents a divalent group represented by the following formula (1-5).
• Q 1 represents a divalent organic group having at least one selected from an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring.
• R 1 to R 5 are each independently an alkyl group having 1 to 10 carbon atoms, which may be interrupted by a hydrogen atom, an oxygen atom, or a sulfur atom.
• R 1 to R 5 represents an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group or a phenyl group.
• the phenyl group is at least one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms. It may be substituted with a monovalent group.
• R 1 and R 2 may be bonded to each other to form a ring having 3 to 6 carbon atoms.
• R 3 and R 4 may be bonded to each other to form a ring having 3 to 6 carbon atoms. It may form three to six rings.
• Z 3 represents a single bond or a divalent group represented by the following formula (1-5). * represents a bond.
• *1 represents a bond bonded to the carbon atom in formula (1).
• *2 represents a bond bonded to the nitrogen atom in formula (1).
• m1 is an integer from 0 to 4
• m2 is 0 or 1
• m3 is 0 or 1
• m4 is an integer from 0 to 2.
• m3 is 1 In the case of , m1 and m2 do not become 0 at the same time.
• *3 represents the bond bonded to the nitrogen atom in formula (1) or formula (1-4).
• *4 represents the bond.
• the alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or sulfur atom in R 1 to R 5 of formulas (1-1) to (1-3) is, for example, an alkyl group having 1 to 10 carbon atoms.
• Examples include groups.
• the alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom may contain two or more oxygen atoms or sulfur atoms.
• X 1 in formula (1) is preferably represented by formula (1-3) or formula (1-4).
• Examples of formula (1) include the structures illustrated below. In the above structure, * represents a bond.
• Q 1 represents a divalent organic group having at least one selected from an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring.
• the aromatic hydrocarbon ring may be monocyclic or polycyclic.
• the aromatic hydrocarbon ring is not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and the like.
• the aliphatic hydrocarbon ring may be monocyclic or polycyclic.
• the aliphatic hydrocarbon ring is not particularly limited and includes, for example, a cyclohexane ring.
• Q 1 is preferably represented by the following formula (2-1).
• Q 11 represents a divalent organic group represented by any of the following formulas (2-1-1) to (2-1-4).
• n1 and n2 are , each independently represents 0 or 1. * represents a bond.
• R 21 to R 26 are each independently a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and 2 to 6 carbon atoms.
• n3 represents 0 or 1. When n3 is 0, n11 represents an integer from 0 to 4. When n3 is 1, n11 represents an integer from 0 to 6.
• R21 When R21 is 2 or more, two or more R21 's may be the same or different.
• Z 4 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms.
• n12 and n13 each independently represent an integer of 0 to 4.
• R22 is 2 or more, two or more R22 's may be the same or different.
• R23 When R23 is 2 or more, two or more R23 's may be the same or different.
• n14 represents an integer from 0 to 4.
• R24 When R24 is 2 or more, two or more R24s may be the same or different.
• Z 5 represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group having 1 to 6 carbon atoms.
• n15 and n16 each independently represent an integer of 0 to 4.
• R25 is 2 or more, two or more R25 's may be the same or different.
• R26 is 2 or more, two or more R26 's may be the same or different.
• examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the alkyl group is not limited to a straight chain, but may be branched or cyclic.
• Examples of the straight-chain or branched alkyl group include methyl group, ethyl group, isopropyl group, tert-butyl group, n-hexyl group, and the like.
• examples of the cyclic alkyl group (cycloalkyl group) include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
• examples of the alkoxy group include methoxy group, ethoxy group, n-pentyloxy group, and isopropoxy group.
• examples of the alkylthio group include methylthio group, ethylthio group, n-pentylthio group, and isopropylthio group.
• examples of alkenyl groups include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2 -Methyl-1-propenyl group, 2-methyl-2-propenyl group, etc.
• examples of the alkynyl group include groups in which the double bond of the alkenyl group listed in the above "alkenyl group” is replaced with a triple bond.
• examples of the alkenyloxy group include vinyloxy group, 1-propenyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, and prenyloxy group.
• examples of the alkynyloxy group include 2-propynyloxy group, 1-methyl-2-propynyloxy group, 2-methyl-2-propynyloxy group, 2-butynyloxy group, 3-butynyloxy group, etc. Can be mentioned.
• examples of the acyl group include an acetyl group and a propionyl group.
• examples of the aryloxy group include phenoxy group, naphthyloxy, and the like.
• examples of the arylcarbonyl group include a phenylcarbonyl group.
• examples of the aralkyl group include a benzyl group and a phenethyl group.
• examples of alkylene groups include methylene group, ethylene group, 1,3-propylene group, 2,2-propylene group, 1-methylethylene group, 1,4-butylene group, and 1-ethylethylene group.
• Examples of the structure represented by formula (2-1) include the structures illustrated below.
• * represents a bond.
• the first component is preferably a compound containing at least one selected from a structure represented by the following formula (11) and a structure represented by the following formula (12). Furthermore, the first component is selected from the structure represented by formula (1), the structure represented by formula (2), the structure represented by formula (11), and the structure represented by formula (12). It is preferable that the compound contains at least one of the following.
• X 1 represents a group represented by any of the above formulas (1-1) to (1-3) and the following formula (1-4A).
• Z 1 and Z 2 each independently represents a single bond or a divalent group represented by the above formula (1-5) (however, *3 in formula (1-5) represents the nitrogen atom in formula (11)). ).
• a 1 , A 2 , A 3 , A 4 , A 5 and A 6 each independently represent a hydrogen atom, a methyl group, or an ethyl group. * represents a bond.
• Q 11 represents a divalent organic group represented by any of the above formulas (2-1-1) to (2-1-4).
• n1 and n2 each independently represent 0 or 1.
• a 11 , A 12 , A 13 , A 14 , A 15 and A 16 each independently represent a hydrogen atom, a methyl group or an ethyl group. * represents a bond.
• Z 3 represents a single bond or a divalent group represented by the above formula (1-5) (However, *3 in the above formula (1-5) represents the formula ( 1-4A).
• a 7 , A 8 and A 9 each independently represent a hydrogen atom, a methyl group or an ethyl group. * represents a bond *1 represents the bond bonded to the carbon atom in formula (11). *2 represents the bond bonded to the nitrogen atom in formula (11).)
• the first component preferably includes at least one of a structure represented by the following formula (E-1) and a structure represented by the following formula (E-2).
• E-1 a structure represented by the following formula (E-1)
• E-2 a structure represented by the following formula (E-2).
• the first component has a plurality of structures represented by the formula (E-1) and the structure represented by the formula (E-2). It is more preferable to have 3 to 3.
• the molecular weight of the first component is not particularly limited. From the viewpoint of solubility in water, it is preferable that the weight average molecular weight of the first component is small.
• the weight average molecular weight of the first component is, for example, 300 to 100,000, preferably 300 to 50,000, more preferably 300 to 10,000, particularly preferably 300 to 5,000.
• X 1 represents a group represented by any of the above formulas (1-1) to (1-3) and the following formula (1-4B).
• Z 1 and Z 2 each independently represents a single bond or a divalent group represented by the above formula (1-5) (however, *3 in formula (1-5) represents the nitrogen atom in formula (11A)).
• A1 , A2 , A3 , A4 , A5 and A6 each independently represent a hydrogen atom, a methyl group or an ethyl group.
• Q 11 represents a divalent organic group represented by any of the above formulas (2-1-1) to (2-1-4).
• n1 and n2 each independently represent 0 or 1.
• a 11 , A 12 , A 13 , A 14 , A 15 and A 16 each independently represent a hydrogen atom, a methyl group or an ethyl group.
• Z 3 represents a single bond or a divalent group represented by formula (1-5) above (However, *3 in formula (1-5) represents formula (1-5) -4B)).
• a 7 , A 8 and A 9 each independently represent a hydrogen atom, a methyl group or an ethyl group.
• *1 represents the formula (11A)
• *2 represents the bond bonded to the nitrogen atom in formula (11A).
• Examples of the compound represented by formula (11A) include the following compounds.
• Examples of the compound represented by formula (12A) include the following compounds.
• X 1 represents a group represented by any of the above formulas (1-1) to (1-3) and the following formula (1-4C).
• Z 1 and Z 2 each independently represents a single bond or a divalent group represented by the above formula (1-5) (however, *3 in formula (1-5) is a nitrogen atom in formula (11B)) (Represents the bonding hand that joins.)
• Q 11 represents a divalent organic group represented by any of the above formulas (2-1-1) to (2-1-4).
• n1 and n2 each independently represent 0 or 1.
• Z 3 represents a single bond or a divalent group represented by formula (1-5) above (However, *3 in formula (1-5) represents formula (1-5) -4C).
• *1 represents the bond bonded to the carbon atom in formula (11B).
• *2 represents the bond bonded to the nitrogen atom in formula (11B). (Represents a bond.)
• Examples of the compound represented by formula (11B) include the following compounds.
• Examples of the compound represented by formula (12B) include the following compounds.
• the divalent organic group may be, for example, a divalent organic group having 1 to 20 carbon atoms, or a divalent organic group having 1 to 10 carbon atoms.
• the divalent organic group may have a heteroatom. Examples of the heteroatom include an oxygen atom and a sulfur atom. Examples of divalent organic groups include hydrocarbon groups having 1 to 10 carbon atoms.
• the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
• Examples of the divalent organic group include a hydroxy group or a hydrocarbon group having 1 to 10 carbon atoms substituted with a mercapto group.
• Examples of the hydrocarbon group include aliphatic hydrocarbon groups.
• Examples of the divalent organic group include a hydrocarbon group having 2 to 10 carbon atoms interrupted by an oxygen atom or a sulfur atom.
• Examples of the hydrocarbon group include aliphatic hydrocarbon groups.
• Examples of the compound represented by formula (EC) include the following compounds.
• Reactions (I) to (III) may be performed, for example, in the presence of a catalyst.
• the catalyst is, for example, a quaternary phosphonium salt such as tetrabutylphosphonium bromide or ethyltriphenylphosphonium bromide, or a quaternary ammonium salt such as benzyltriethylammonium chloride.
• the amount of the catalyst to be used can be selected from a range of 0.1 to 10% by mass based on the total mass of the polymer raw materials used in the reaction.
• the optimum temperature and time for the polymerization reaction can be selected from the range of, for example, 80 to 160° C. and 2 to 50 hours.
• the second component is used to improve the coating properties of the composition for forming a resist underlayer film.
• the second component is a water-soluble polymer.
• the second component is a different compound than the first component.
• the water-soluble polymer is a polymer compound that dissolves 1 g or more in 100 g of water at 25°C, and preferably a polymer compound that dissolves 5 g or more in 100 g of water at 25°C. It is more preferable to use a polymer compound that can dissolve 10 g or more in water.
• water-soluble polymers include, but are not limited to, polyvinyl alcohol, water-soluble cellulose, polyethylene glycol (PEG), polyethylene oxide (PEO), polyvinylpyrrolidone, polyacrylic acid, polystyrene sulfonic acid, polyvinylacetamide, and the like.
• Polyvinyl alcohol is a polymer obtained by hydrolyzing polyvinyl acetate to change the acetyl groups in the polyvinyl acetate molecules to hydroxyl groups.
• the value expressed in mol% of this proportion of hydroxyl groups is called the degree of saponification.
• Polyvinyl alcohol is known to have various properties depending on its degree of saponification. For example, polyvinyl acetate (saponification degree of 0% by mole) is generally known to be water-insoluble, and polyvinyl alcohol having a saponification degree of 100% by mole is known to be water-soluble.
• polyvinyl alcohols if the degree of saponification is 60 mol% or less, the solubility in water is poor, and if the degree of saponification is 30 mol% or less, there is substantially no dissolution. On the other hand, if the degree of saponification is too high, the solubility will be low, and a degree of 85 to 90 mol% has the highest solubility. In the present invention, it is preferable to use polyvinyl alcohol having a degree of saponification of 70 mol% or more. Generally, the higher the degree of saponification, the better the developer resistance, so it is preferable to use polyvinyl alcohol with a degree of saponification of 75 mol% or more.
• the degree of saponification of polyvinyl alcohol is preferably 99 mol% or less, and 98 mol%. The following are more preferable.
• the degree of polymerization of polyvinyl alcohol is usually expressed as the viscosity of a 4% by mass aqueous solution (20°C), and is generally about 1 to 80 cps (mPa ⁇ s).
• these polyvinyl alcohols used in the present invention those having a viscosity of 1 cps or more are preferable, and those having a viscosity of 2 cps or more are more preferable.
• the upper limit of the viscosity is preferably 70 cps, and the upper limit of the viscosity is more preferably 65 cps, 50 cps, 40 cps, 30 cps, 20 cps, 10 cps, 8 cps, or 5 cps.
• the range of viscosity is, for example, 1 to 20 cps, 2 to 10 cps, and 3 to 8 cps.
• the polyvinyl alcohol may be modified by having some of its hydroxyl groups substituted with an alkyl ether group, an alkyloxymethyl group, an acetyl acetate group, or the like.
• water-soluble cellulose examples include, but are not particularly limited to, alkyl celluloses such as methyl cellulose and ethyl cellulose; hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose; hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose and hydroxypropyl methyl cellulose. . Among these, hydroxypropyl cellulose is more preferred.
• hydroxypropyl cellulose products with different viscosities are commercially available from various companies, and any of them can be used in the present invention.
• the viscosity of a 2% by mass aqueous solution (20°C) of hydroxypropyl cellulose is not particularly limited and can be selected as appropriate depending on the purpose, but it is 2.0 mPa ⁇ s (centipoise, cps) or more and 4,000 mPa ⁇ s ( Centipoise (cps) or less is preferable. Further, the viscosity of hydroxypropylcellulose is considered to depend on the weight average molecular weight, degree of substitution, and molecular weight of hydroxypropylcellulose.
• the weight average molecular weight of hydroxypropyl cellulose is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 15,000 or more and 400,000 or less. Note that the weight average molecular weight can be measured using, for example, gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• hydroxypropyl cellulose are not particularly limited and can be appropriately selected depending on the purpose, and examples include the following commercial products.
• ⁇ HPC-SSL, etc. manufactured by Nippon Soda Co., Ltd.
• a molecular weight of 15,000 to 30,000 and a viscosity of 2.0 mPa ⁇ s to 2.9 mPa ⁇ s ⁇ HPC-SL, etc.
• a molecular weight of 30,000 to 50,000 and a viscosity of 3.0 mPa ⁇ s to 5.9 mPa ⁇ s ⁇ HPC-L, etc.
• HPC-SSL having a molecular weight of 15,000 to 30,000 and a viscosity of 2.0 mPa ⁇ s to 2.9 mPa ⁇ s is preferred.
• a molecular weight is measured using gel permeation chromatography (GPC), and a viscosity is measured using 2 mass % aqueous solution (20 degreeC).
• Polystyrene sulfonic acid is not particularly limited as long as it exhibits water solubility, and its sulfonation rate may be 100% or less than 100%.
• the sulfonation rate is, for example, 80% or more and 100% or less.
• “sulfonation rate” refers to the mole of "styrene units having a sulfonic acid group" out of the total of "styrene units having a sulfonic acid group” and "styrene units" in the molecule in polystyrene sulfonic acid. Refers to percentage (%).
• polystyrene sulfonic acid may be a homopolymer consisting only of repeating units represented by the following formula (SS), or may be a homopolymer consisting only of repeating units represented by the formula (SS) and the following formula (St). It may also be a copolymer having repeating units.
• Examples of the styrene sulfonic acid constituting polystyrene sulfonic acid include 4-styrene sulfonic acid.
• the content of the second component (water-soluble polymer) in the composition for forming a resist underlayer film is not particularly limited.
• the mass ratio of the first component to the second component (first component: second component) in the composition for forming a resist underlayer film is preferably 99:1 to 50:50, and 99:1.
• the ratio is more preferably 75:25, and particularly preferably 99:1 to 90:10.
• the composition for forming a resist underlayer film preferably contains a crosslinking agent.
• the crosslinking agent included as an optional component in the composition for forming a resist underlayer film has, for example, a functional group that reacts by itself.
• crosslinking agent examples include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (tetramethoxymethylglycoluril) (POWDERLINK [registered trademark] 1174), 1, 3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis Examples include (butoxymethyl)urea and 1,1,3,3-tetrakis(methoxymethyl)urea.
• crosslinking agent is a nitrogen-containing compound having 2 to 6 substituents in one molecule represented by the following formula (1d) that bond to a nitrogen atom, as described in International Publication No. 2017/187969. Good too.
• R 1 represents a methyl group or an ethyl group. * represents a bond bonded to a nitrogen atom.
• the nitrogen-containing compound having 2 to 6 substituents represented by the formula (1d) in one molecule may be a glycoluril derivative represented by the following formula (1E).
• R 1 's 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 the formula (1E) examples include compounds represented by the following formulas (1E-1) to (1E-6).
• a nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1d) in one molecule has 2 to 6 substituents represented by the following formula (2d) bonded to a nitrogen atom in one molecule. It can be obtained by reacting a nitrogen-containing compound with at least one compound represented by the following formula (3d).
• R 1 represents a methyl group or ethyl group
• R 4 represents an alkyl group having 1 to 4 carbon atoms. * represents a bond bonded to a nitrogen atom.
• the glycoluril derivative represented by the formula (1E) can be obtained by reacting the glycoluril derivative represented by the following formula (2E) with at least one compound represented by the formula (3d).
• the nitrogen-containing compound having 2 to 6 substituents represented by the formula (2d) in one molecule is, for example, a glycoluril derivative represented by the following formula (2E).
• R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R 4 each independently represents an alkyl group having 1 to 4 carbon atoms.
• glycoluril derivative represented by the formula (2E) examples include compounds represented by the following formulas (2E-1) to (2E-4). Furthermore, examples of the compound represented by the formula (3d) include compounds represented by the following formula (3d-1) and formula (3d-2).
• crosslinking agent may be a crosslinking compound represented by the following formula (G-1) or formula (G-2) described in International Publication No. 2014/208542.
• Q 1 represents a single bond or a monovalent organic group
• R 1 and R 4 each have a carbon atom number having an alkyl group having 2 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. It represents an alkyl group having 2 to 10 carbon atoms
• R 2 and R 5 each represent a hydrogen atom or a methyl group
• R 3 and R 6 each represent an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms. Indicates the group.
• n1 is an integer of 1 ⁇ n1 ⁇ 3, n2 is an integer of 2 ⁇ n2 ⁇ 5, n3 is an integer of 0 ⁇ n3 ⁇ 3, n4 is an integer of 0 ⁇ n4 ⁇ 3, and an integer of 3 ⁇ (n1+n2+n3+n4) ⁇ 6.
• n5 is an integer of 1 ⁇ n5 ⁇ 3, n6 is an integer of 1 ⁇ n6 ⁇ 4, n7 is an integer of 0 ⁇ n7 ⁇ 3, n8 is an integer of 0 ⁇ n8 ⁇ 3, and an integer of 2 ⁇ (n5+n6+n7+n8) ⁇ 5.
• m1 represents an integer from 2 to 10.
• the crosslinkable compound represented by the above formula (G-1) or formula (G-2) is a compound represented by the following formula (G-3) or formula (G-4), and a hydroxyl group-containing ether compound or a carbon atom. It may be obtained by reaction with several 2 to 10 alcohols.
• Q 2 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, and R 7 and R 10 each have 1 carbon atom. It represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.
• n9 is an integer of 1 ⁇ n9 ⁇ 3, n10 is an integer of 2 ⁇ n10 ⁇ 5, n11 is an integer of 0 ⁇ n11 ⁇ 3, n12 is an integer of 0 ⁇ n12 ⁇ 3, and an integer of 3 ⁇ (n9+n10+n11+n12) ⁇ 6. show.
• n13 is an integer of 1 ⁇ n13 ⁇ 3
• n14 is an integer of 1 ⁇ n14 ⁇ 4
• n15 is an integer of 0 ⁇ n15 ⁇ 3
• n16 is an integer of 0 ⁇ n16 ⁇ 3
• m2 represents an integer from 2 to 10.
• Me represents a methyl group.
• the content of the crosslinking agent in the composition for forming a resist underlayer film is, for example, 1% by mass to 50% by mass based on the total of the first component and the second component, Preferably, it is 5% by mass to 40% by mass. Further, when the crosslinking agent is used, the content of the crosslinking agent in the composition for forming a resist underlayer film is, for example, 1% by mass to 50% by mass with respect to the total of the first component, and preferably, It is 5% by mass to 40% by mass.
• ⁇ Curing catalyst> As the curing catalyst contained as an optional component in the composition for forming a resist underlayer film, either a thermal acid generator or a photoacid generator can be used, but it is preferable to use a thermal acid generator.
• thermal acid generator examples include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridiniumphenolsulfonic acid, and pyridinium-p-hydroxybenzenesulfonic acid (pyridinium-p-toluenesulfonic acid).
• p-phenolsulfonic acid pyridinium salt pyridinium-trifluoromethanesulfonic acid
• salicylic acid camphorsulfonic acid
• 5-sulfosalicylic acid 4-chlorobenzenesulfonic acid
• 4-hydroxybenzenesulfonic acid 4-hydroxybenzenesulfonic acid
• benzenedisulfonic acid 1-naphthalenesulfonic acid
• Examples include sulfonic acid compounds and carboxylic acid compounds such as citric acid, benzoic acid, and hydroxybenzoic acid.
• Examples of the photoacid generator include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.
• onium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butanesulfonate, diphenyliodonium perfluoronormal octane sulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl) Iodonium salt compounds such as iodonium camphorsulfonate and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium Examples include sulfonium salt compounds such
• sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide. Can be mentioned.
• disulfonyldiazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, and bis(2,4-dimethylbenzenesulfonyl). ) diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.
• the content of the curing catalyst is, for example, 0.1% to 50% by weight, preferably 1% to 30% by weight, based on the crosslinking agent.
• the composition for forming a resist underlayer film contains a solvent.
• the solvent includes water.
• the solvent may contain an organic solvent in addition to water.
• the solvent preferably contains 50% by mass or more of water based on the solvent, more preferably contains 70% by mass or more of water based on the solvent, and even more preferably contains 80% by mass or more of water based on the solvent. , particularly preferably 90% by mass or more of water based on the solvent.
• organic solvents organic solvents generally used in chemical solutions for semiconductor lithography processes are preferred. 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, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, 2-hydroxyisobutyric acid Ethyl, ethyl ethoxy acetate, 2-hydroxyethyl e
• propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred. Particularly preferred are propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.
• a surfactant can be further added to the composition for forming a resist underlayer film in order to prevent occurrence of pinholes, striations, etc., and to further improve coating properties against surface unevenness.
• surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and polyoxyethylene nonylphenol ether.
• sorbitan fatty acid esters polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc.
• Nonionic surfactants such as fatty acid esters, FTOP EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade name), Megafac F171, F173, R-30 (manufactured by DIC Corporation, trade name) , Fluorade FC430, FC431 (manufactured by Sumitomo 3M Ltd., product name), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., product name), etc.
• fatty acid esters such as fatty acid esters, FTOP EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade name), Megafac F171, F173, R-30 (manufactured by DIC Corporation, trade name) , Fluorade FC430, FC431 (manufactured by
• surfactants organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
• the blending amount of these surfactants is not particularly limited, but is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on the total solid content of the composition for forming a resist underlayer film.
• These surfactants may be added alone or in combination of two or more.
• the film constituent components contained in the composition for forming a resist underlayer film are, for example, 0.01% by mass to 10% by mass of the composition for forming a resist underlayer film.
• the composition for forming a resist underlayer film of the present invention is produced, for example, by a method of mixing the first component, a solvent, etc. by a known method.
• the manufactured composition is preferably filtered using a filter or the like in order to remove metal impurities, foreign substances, etc. present in the composition.
• One of the measures for evaluating whether the composition for forming a resist underlayer film is in a uniform solution state is to observe the permeability of a specific microfilter. It is preferable that the substance pass through a microfilter with a pore size of 0.1 ⁇ m, 0.05 ⁇ m, 0.03 ⁇ m, 0.02 ⁇ m, or 0.01 ⁇ m and exhibit a uniform solution state.
• the materials for the microfilter include PTFE (polytetrafluoroethylene), fluororesins such as PFA (tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer), PE (polyethylene), UPE (ultra high molecular weight polyethylene), and PP. (polypropylene), PSF (polysulfone), PES (polyethersulfone), and nylon, but it is preferably made of PTFE (polytetrafluoroethylene). Since the composition for forming a resist underlayer film contains water as a solvent, the filter used for filtering the composition for forming a resist underlayer film is preferably a filter that has been subjected to a hydrophilic treatment.
• PFA tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer
• PE polyethylene
• UPE ultra high molecular weight polyethylene
• PP. polypropylene
• PSF polysulfone
• PES polyethers
• the resist underlayer film of the present invention is a cured product of the above-described composition for forming a resist underlayer film.
• the resist underlayer film can be manufactured, for example, by applying the above-described composition for forming a resist underlayer film onto a semiconductor substrate and baking it.
• Examples of the semiconductor substrate to which the composition for forming a resist underlayer film is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.
• the inorganic film can be formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum evaporation. method, spin coating method (spin-on-glass: SOG).
• ALD atomic layer deposition
• CVD chemical vapor deposition
• reactive sputtering ion plating
• vacuum evaporation. method spin coating method (spin-on-glass: SOG).
• spin-on-glass: SOG spin coating method
• the inorganic film include a polysilicon film, a silicon oxide film, a silicon nitride film, a BPSG (Boro-Phospho Silicate Glass) film, a titanium nitride film, a titanium nitride oxide film, a tungsten film, a gallium nitride film, and a gallium arsenide film. can be mentioned.
• the inorganic film may be a single layer or a multilayer of two or more layers. In the case of multiple layers or more, each layer may be the same type of inorganic film or may be a different type of inorganic film.
• the thickness of the inorganic film is not particularly limited.
• the composition for forming a resist underlayer film of the present invention is applied onto such a semiconductor substrate using a suitable coating method such as a spinner or a coater. Thereafter, a resist lower layer film is formed by baking using a heating means such as a hot plate.
• the baking conditions are appropriately selected from baking temperatures of 100° C. to 400° C. and baking times of 0.3 minutes to 60 minutes.
• the baking temperature is 120°C to 350°C and the baking time is 0.5 to 30 minutes, more preferably the baking temperature is 150°C to 300°C, and the baking time is 0.8 to 10 minutes.
• the thickness of the resist underlayer film is, 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) ⁇ 0.05 ⁇ m (50 nm), 0.003 ⁇ m (3 nm) ⁇ 0.05 ⁇ m (50 nm), 0.004 ⁇ m (4 nm) ⁇ 0.05 ⁇ m (50 nm), 0.
• the method for measuring the thickness of the resist underlayer film in this specification is as follows. ⁇ Measuring device name: Optical interference film thickness meter (Product name: Nanospec 6100, manufactured by Nanometrics Japan Co., Ltd.) - Arithmetic average of 4 points (for example, 4 points measured at 1 cm intervals in the wafer X direction)
• a substrate for semiconductor processing of the present invention includes a semiconductor substrate and a resist underlayer film of the present invention.
• the semiconductor substrate include the aforementioned semiconductor substrates.
• the resist underlayer film is disposed on a semiconductor substrate.
• the method for manufacturing a semiconductor device of the present invention includes at least the following steps. ⁇ A step of forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film of the present invention, and ⁇ A step of forming a resist film on the resist underlayer film.
• the pattern forming method of the present invention includes at least the following steps. - Forming a resist underlayer film on a semiconductor substrate using the composition for forming a resist underlayer film of the present invention, ⁇ Process of forming a resist film on the resist lower layer film ⁇ Process of irradiating the resist film with light or electron beam and then developing the resist film to obtain a resist pattern; ⁇ Using the resist pattern as a mask, forming the resist film Process of etching the lower layer film
• a resist film is formed on the resist underlayer film.
• the thickness of the resist film is preferably 200 nm or less, more preferably 150 nm or less, even more preferably 100 nm or less, and particularly preferably 80 nm or less. Further, the thickness of the resist film is preferably 10 nm or more, more preferably 20 nm or more, and particularly preferably 30 nm or more.
• the resist film formed on the resist underlayer film by a known method is not particularly limited as long as it responds to the light or electron beam (EB) used for irradiation.
• EB light or electron beam
• Both negative photoresists and positive photoresists can be used.
• the light or electron beam is not particularly limited, but examples include i-line (365 nm), KrF excimer laser (248 nm), ArF excimer laser (193 nm), EUV (extreme ultraviolet; 13.5 nm), and EB (electron beam). Can be mentioned. Note that in this specification, a resist that responds to EB is also referred to as a photoresist.
• photoresists there are positive type photoresists made of novolac resin and 1,2-naphthoquinonediazide sulfonic acid ester, and chemically amplified type made of a photoacid generator and a binder having a group that decomposes with acid to increase the alkali dissolution rate.
• Photoresist a chemically amplified photoresist consisting of a low-molecular compound, an alkali-soluble binder, and a photoacid generator that decomposes with acid to increase the alkali dissolution rate of the photoresist, and a chemically amplified photoresist that decomposes with acid to increase the alkali dissolution rate.
• photoresists made of a binder having a group, a low-molecular compound that is decomposed by acid to increase the alkali dissolution rate of the photoacid generator, and a photoacid generator, and resists containing metal elements.
• Examples include product name V146G manufactured by JSR Corporation, product name APEX-E manufactured by Shipley, product name PAR710 manufactured by Sumitomo Chemical Co., Ltd., and product names AR2772 and SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd.
• Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000) a fluorine-containing atom polymer photoresist can be mentioned.
• Examples of the resist composition include the following compositions.
• Resin A having a repeating unit having an acid-decomposable group whose polar group is protected with a protecting group that is removed by the action of an acid, and an actinic ray-sensitive or Radiation sensitive resin composition.
• 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 -.
• L 2 represents an alkylene group that may have a substituent or a single bond.
• W 1 represents a cyclic organic group which may have a substituent.
• M + represents a cation.
• 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 group having 1 to 20 carbon atoms. It is a monovalent organic group.
• n is an integer from 0 to 11. When n is 2 or more, plural R 1 are the same or different.
• R 2 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoro It is a methyl group.
• R 3 is a monovalent group having 1 to 20 carbon atoms and containing the above 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 is a single bond
• -CO-O-* or -CO-NR 4 - * represents a bond with -Ar
• R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• Ar is one or more selected from the group consisting of a hydroxy group and a carboxyl group.
• Examples of the resist film include the following.
• 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, a naphthylene group, an ester bond, a lactone ring, It is a linking group having 1 to 12 carbon atoms and containing at least one selected from phenylene group and naphthylene group.
• X 2 is a single bond, ester bond, or amide bond.
• resist materials include the following.
• 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 carbon An alkylene group having 1 to 12 atoms or an arylene group having 6 to 10 carbon atoms, even if a part of the methylene group constituting the alkylene group is substituted with an ether group, ester group, or lactone ring-containing group. Often, at least one hydrogen atom contained in X 2 is substituted with a bromine atom.
• Rf 1 to Rf 4 are each independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, at least one of which is a fluorine atom or a trifluoromethyl group.Also, Rf 1 and Rf 2 may be combined 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, and some or all of the
• R 1 and R 2 may be bonded together to form a ring with the sulfur atom to which they are bonded. Also good.
• 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 carbon atom number 1 ⁇ 6 alkyl group, or a halogen atom other than bromine. ⁇ 12 alkylene group.
• 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 (However, m+u is an integer from 1 to 4.)
• a resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid Contains a base material component (A) whose solubility in a developer changes due to the action of an acid and a fluorine additive component (F) which shows decomposition properties in an alkaline developer,
• the fluorine additive component (F) is a fluorine additive 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 is each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group, or a cyano group.
• n is an integer from 0 to 2. * is 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 that does not have an 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.
• Each R 2 is independently an organic group having a fluorine atom.
• coatings examples include the following.
• Coatings comprising metal oxo-hydroxo networks with organic ligands via metal carbon bonds and/or metal carboxylate bonds.
• a coating solution comprising an organic solvent and a first organometallic compound represented by the formula RSnO (3/2-x/2) (OH) x (where 0 ⁇ x ⁇ 3), the coating solution comprising: from about 0.0025 M to about 1.5 M tin, R is an alkyl group or cycloalkyl group having 3 to 31 carbon atoms, and the alkyl group or cycloalkyl group is secondary or secondary. Coating solution, bonded to tin at the tertiary carbon atom.
• An aqueous inorganic patterning precursor solution comprising a mixture of water, a metal suboxide cation, a polyatomic inorganic anion, 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.
• the exposure amount and the electron beam irradiation energy are not particularly limited.
• Post Exposure Bake may be performed after irradiation with light or electron beams and before development.
• the baking temperature is not particularly limited, but is preferably 60°C to 150°C, more preferably 70°C to 120°C, and particularly preferably 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 for development.
• the developing temperature is, for example, 5°C to 50°C.
• the developing time is, for example, 10 seconds to 300 seconds.
• alkaline developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and secondary amines such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline.
• Aqueous solutions of alkalis such as quaternary ammonium salts, cyclic amines such as pyrrole and piperidine, etc. can be used. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the aqueous solution of the alkali.
• preferred developing solutions are aqueous solutions of quaternary ammonium salts, more preferably aqueous solutions of tetramethylammonium hydroxide and aqueous solutions of choline.
• surfactants and the like can also be added to these developers. It is also possible to use a method in which the photoresist is developed with an organic solvent such as butyl acetate instead of the alkaline developer, and the portions of the photoresist where the alkali dissolution rate has not been improved are developed.
• the resist underlayer film is etched using the formed resist pattern as a mask. Etching may be dry etching or wet etching, but dry etching is preferable. If the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed; if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. let Thereafter, a semiconductor device can be manufactured by processing the semiconductor substrate by a known method (such as dry etching).
• the weight average molecular weights of the polymers shown in Synthesis Examples 1 to 10 below are the results of measurements by gel permeation chromatography (hereinafter abbreviated as GPC).
• GPC gel permeation chromatography
• a reaction flask containing 24.52 g of propylene glycol monomethyl ether (propylene glycol monomethyl ether) was heated and stirred at 105° C. for 18 hours under a nitrogen atmosphere.
• the obtained reaction product corresponded to the following formula (X-1), and had a weight average molecular weight Mw of 330 as measured by GPC in terms of polystyrene. Thereafter, a solution of the reaction product was dropped into a hexane solution, and the resulting precipitate was collected by filtration and dried under vacuum at 40°C. The obtained compound was dissolved in ultrapure water to a concentration of 10% by mass.
• the obtained reaction product corresponded to the following formula (X-3), and had a weight average molecular weight Mw of 500 as measured by GPC in terms of polystyrene. Thereafter, a solution of the reaction product was dropped into a hexane solution, and the resulting precipitate was collected by filtration and dried under vacuum at 40°C. The obtained compound was dissolved in ultrapure water to a concentration of 10% by mass.
• the reaction flask to which 37.10 g of ether was added was heated and stirred at 105° C. for 18 hours under a nitrogen atmosphere.
• the obtained reaction product corresponded to the following formula (X-4), and the weight average molecular weight Mw measured in terms of polystyrene by GPC was 700. Thereafter, a solution of the reaction product was dropped into a hexane solution, and the resulting precipitate was collected by filtration and dried under vacuum at 40°C.
• the obtained compound was dissolved in ultrapure water to a concentration of 10% by mass.
• the reaction flask to which 47 g was added was heated and stirred at 105° C. for 22 hours under a nitrogen atmosphere.
• the obtained reaction product corresponded to the following formula (X-6), and the weight average molecular weight Mw measured in terms of polystyrene by GPC was 400. Thereafter, a solution of the reaction product was dropped into a hexane solution, and the resulting precipitate was collected by filtration and dried under vacuum at 40°C. The obtained compound was dissolved in ultrapure water to a concentration of 10% by mass.
• ⁇ Synthesis example 9> 2.16 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.00 g of glycidol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and 0.22 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Co., Ltd.), and 17 g of propylene glycol monomethyl ether.
• the reaction flask to which 0.54 g was added was heated and stirred at 105° C. for 22 hours under a nitrogen atmosphere.
• the obtained reaction product corresponded to formula (x-9), and had a weight average molecular weight Mw of 450 as measured by GPC in terms of polystyrene. Thereafter, a solution of the reaction product was dropped into a hexane solution, and the resulting precipitate was collected by filtration and dried under vacuum at 40°C. The obtained compound was dissolved in ultrapure water to a concentration of 10% by mass.
• the obtained reaction product corresponded to the following formula (X-2), and had a weight average molecular weight Mw of 530 as measured by GPC in terms of polystyrene.
• Example 1 To 7.33 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 1, 0.18 g of tetramethoxymethyl glycoluril and 0.0 g of pyridinium p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. 02 g, hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.) 0.03 g, and 92.41 g of ultrapure water were added to form a solution. The solution was filtered using a hydrophilized PTFE syringe filter with a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• HPC-SSL hydroxypropyl cellulose
• Example 2 To 7.33 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 2, 0.18 g of tetramethoxymethyl glycoluril and 0.0 g of pyridinium p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. 02 g, hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.) 0.03 g, and 92.41 g of ultrapure water were added to form a solution. The solution was filtered using a hydrophilized PTFE syringe filter with a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• HPC-SSL hydroxypropyl cellulose
• Example 3 To 7.33 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 3, 0.18 g of tetramethoxymethyl glycoluril and 0.0 g of pyridinium p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. 02 g, hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.) 0.03 g, and 92.41 g of ultrapure water were added to form a solution. The solution was filtered using a hydrophilized PTFE syringe filter with a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• HPC-SSL hydroxypropyl cellulose
• Example 4 To 7.33 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 4, 0.18 g of tetramethoxymethyl glycoluril and 0.0 g of pyridinium p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. 02 g, hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.) 0.03 g, and 92.41 g of ultrapure water were added to form a solution. The solution was filtered using a hydrophilized PTFE syringe filter with a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• HPC-SSL hydroxypropyl cellulose
• Example 5 To 7.33 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 5, 0.18 g of tetramethoxymethyl glycoluril and 0.0 g of pyridinium p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. 02 g, hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.) 0.03 g, and 92.41 g of ultrapure water were added to form a solution. The solution was filtered using a hydrophilized PTFE syringe filter with a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• HPC-SSL hydroxypropyl cellulose
• Example 6 To 7.33 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 6, 0.18 g of tetramethoxymethyl glycoluril and 0.0 g of pyridinium p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. 02 g, hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.) 0.03 g, and 92.41 g of ultrapure water were added to form a solution. The solution was filtered using a hydrophilized PTFE syringe filter with a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• HPC-SSL hydroxypropyl cellulose
• Example 7 To 7.33 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 7, 0.18 g of tetramethoxymethyl glycoluril and 0.0 g of pyridinium p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. 02 g, hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.) 0.03 g, and 92.41 g of ultrapure water were added to form a solution. The solution was filtered using a hydrophilized PTFE syringe filter with a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• HPC-SSL hydroxypropyl cellulose
• Example 8 To 7.33 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 8, 0.18 g of tetramethoxymethyl glycoluril and 0.0 g of pyridinium p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. 02 g, hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.) 0.03 g, and 92.41 g of ultrapure water were added to form a solution. The solution was filtered using a hydrophilized PTFE syringe filter with a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• HPC-SSL hydroxypropyl cellulose
• Example 9 To 7.33 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 9, 0.18 g of tetramethoxymethyl glycoluril and 0.0 g of pyridinium p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. 02 g, hydroxypropyl cellulose (HPC-SSL, Nippon Soda Co., Ltd.) 0.03 g, and 92.41 g of ultrapure water were added to form a solution. The solution was filtered using a hydrophilized PTFE syringe filter with a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• HPC-SSL hydroxypropyl cellulose
• Example 10 To 7.33 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 2, 0.18 g of tetramethoxymethyl glycoluril and 0.0 g of pyridinium p-toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. 02 g, polyvinyl alcohol (PXP-05, Nippon Vinyl Alcohol Co., Ltd.), 0.03 g, and 92.41 g of ultrapure water were added to form a solution. The solution was filtered using a hydrophilized PTFE syringe filter with a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• PXP-05 polyvinyl alcohol
• 92.41 g ultrapure water
• Example 11 To 9.19 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 2, 0.03 g of pyridinium trifluoromethanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), hydroxypropyl cellulose (HPC-SSL, 0.05 g of Nippon Soda Co., Ltd.) and 90.72 g of ultrapure water were added to form a solution. The solution was filtered using a hydrophilized PTFE syringe filter with a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• Example 12 To 13.59 g of the aqueous solution (solid content: 10% by mass) of the reaction product obtained in Synthesis Example 2, 0.04 g of polystyrene sulfonic acid (manufactured by Sigma-Aldrich) and 86.36 g of ultrapure water were added, and the solution and did. The solution was filtered using a hydrophilized PTFE syringe filter with a pore size of 0.02 ⁇ m to prepare a composition for forming a resist underlayer film.
• resist solvent resistance test Each of the resist underlayer film forming compositions prepared in Examples 1 to 12 was applied (spin coated) onto a silicon wafer using a spin coater. The coated silicon wafer was heated on a hot plate at 205° C. for 1 minute to form a film (lower layer film) with a thickness of 25 nm. Next, in order to confirm the solvent resistance of the lower layer film, the silicon wafer after the lower layer film was formed was immersed for 1 minute in a mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate in a mass ratio of 7:3. After spin drying, it was baked at 100°C for 30 seconds. The thickness of the protective film before and after immersion in the mixed solvent was measured using an optical interference film thickness meter (product name: Nanospec 6100, manufactured by Nanometrics Japan Co., Ltd.).
• Solvent resistance was evaluated by calculating and evaluating the film thickness reduction rate (%) of the lower layer film removed by solvent immersion using the following formula.
• Film thickness reduction rate (%) ((A-B) ⁇ A) x 100
• Table 1 Note that if the film thickness reduction rate is about 1% or less, it can be said that the film has sufficient solvent resistance.
• the films formed from the resist underlayer film forming compositions of Examples 1 to 12 had very small changes in film thickness even after being immersed in the solvent. Therefore, the films formed from the resist underlayer film forming compositions of Examples 1 to 12 have sufficient solvent resistance to function as underlayer films. Note that in Examples 1, 3, 6, 9, and 11, the film thickness reduction rate was negative, but there was no particular problem.
• a commercially available photoresist solution (manufactured by JSR Corporation, trade name: AR2772) is applied onto this resist underlayer film using a spin coater, and baked on a hot plate (for example, at 110°C for 90 seconds) to thicken the film. A 100 nm photoresist film was formed. Next, using a scanner [manufactured by Nikon Corporation, NSRS307E (wavelength 193 nm, NA: 0.85, ⁇ : 0.85/0.93 (Dipole)]], the line width of the photoresist and the width of the photoresist were measured after development.
• Exposure was performed through a photomask set so that the width between lines was 0.065 ⁇ m, that is, 0.065 ⁇ m L/S (dense lines), and nine such lines were formed.
• PEB post-exposure heating
• a 0.26N tetramethylammonium hydroxide aqueous solution was added as a developer using an industrial standard 60 second single paddle process. It was developed using Through the above process, a resist pattern was formed.
• FIG. 1 shows an SEM image of a cross section of a photoresist pattern finally formed on a substrate using the composition for forming a resist underlayer film of Example 2.

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