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
• • 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
  • G03F7/16—Coating processes; Apparatus therefor
  • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
  • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
• • 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
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/69—Etching of wafers, substrates or parts of devices using masks for semiconductor materials
  • H10P50/691—Etching of wafers, substrates or parts of devices using masks for semiconductor materials for Group V materials or Group III-V materials
  • H10P50/692—Etching of wafers, substrates or parts of devices using masks for semiconductor materials for Group V materials or Group III-V materials characterised by their composition, e.g. multilayer masks or materials
• • 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
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/69—Etching of wafers, substrates or parts of devices using masks for semiconductor materials
  • H10P50/691—Etching of wafers, substrates or parts of devices using masks for semiconductor materials for Group V materials or Group III-V materials
  • H10P50/693—Etching of wafers, substrates or parts of devices using masks for semiconductor materials for Group V materials or Group III-V materials characterised by their size, orientation, disposition, behaviour or shape, in horizontal or vertical plane
  • H10P50/695—Etching of wafers, substrates or parts of devices using masks for semiconductor materials for Group V materials or Group III-V materials characterised by their size, orientation, disposition, behaviour or shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks or sidewalls or to modify the mask
• • 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
  • H10P76/2041—Photolithographic processes
  • H10P76/2042—Photolithographic processes using lasers

Definitions

• the present invention relates to compositions used in lithographic processes in semiconductor manufacturing, particularly in cutting-edge (ArF, EUV, EB, etc.) lithographic processes.
• the present invention also relates to a method of manufacturing a substrate with a resist pattern to which the resist underlayer film is applied, and a method of manufacturing a semiconductor device.
• microfabrication by lithography using a resist composition has been performed in the manufacture of semiconductor devices.
• a thin film of a photoresist composition is formed on a semiconductor substrate such as a silicon wafer, exposed to actinic rays such as ultraviolet rays through a mask pattern on which a device pattern is drawn, and developed.
• actinic rays such as ultraviolet rays
• This is a processing method in which the substrate is etched using the obtained photoresist pattern as a protective film to form fine unevenness corresponding to the pattern on the substrate surface.
• Patent Document 1 discloses a composition for forming a resist underlayer film for EUV lithography containing a condensation polymer.
• Patent Literature 2 discloses an organic film material for forming an organic film having both dry etching resistance and advanced embedding/planarization properties.
• Properties required for the resist underlayer film include, for example, no intermixing with the resist film formed on the upper layer (insolubility in the resist solvent).
• the line width of the formed resist pattern is 32 nm or less, and the resist underlayer film for EUV exposure is formed thinner than before.
• it is difficult to form a defect-free uniform film because pinholes and aggregation are likely to occur due to the influence of the substrate surface, the polymer used, and the like.
• a solvent capable of dissolving the resist film usually an organic solvent, is used to remove the unexposed portion of the resist film, leaving the exposed portion of the resist film as a resist pattern.
• improvement of the adhesion of the resist pattern is a major issue.
• LWR Line Width Roughness, line width roughness, line width fluctuation (roughness)
• An object of the present invention is to provide a composition for forming a resist underlayer film capable of forming a desired resist pattern, and a method for forming a resist pattern using the resist underlayer film-forming composition, which solves the above problems. .
• the present invention includes the following.
• Ar 1 and Ar 2 each independently represent an optionally substituted aromatic ring having 6 to 40 carbon atoms, and at least one of Ar 1 and Ar 2 is a naphthalene ring; , L 1 represents a single bond, an optionally substituted alkylene group having 1 to 10 carbon atoms or an optionally substituted alkenylene group having 2 to 10 carbon atoms, and T 1 and T 2 are each independently represents a single bond, an ester bond or an ether bond, and E represents an epoxy group.) and a compound (A) represented by A resist underlayer film-forming composition comprising a reaction product with a compound (B) containing at least two groups reactive with an epoxy group, and a solvent.
• the compound (B) has the following formula (101): (In formula (101), X 1 is the following formula (2), formula (3), formula (4), or formula (0): (In formulas (2), (3), (4) and (0), R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 10 alkenyl group, benzyl group or phenyl group, and said alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, benzyl group and phenyl group are those having 1 to 6 carbon atoms.
• R 1 and R 2 may be bonded together to form a ring having 3 to 10 carbon atoms, and R 3 is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 2 1 to 10 alkenyl group, benzyl group or phenyl group, and the phenyl group is an alkyl group having 1 to 10 carbon atoms, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a nitro group, a cyano group, a hydroxy and an alkylthio group having 1 to 10 carbon atoms.
• the terminal of the reaction product is represented by the following formula (102):
• Ar represents an optionally substituted aromatic ring having 6 to 40 carbon atoms
• L 1 is an ester bond, an ether bond or an optionally substituted alkenylene having 2 to 10 carbon atoms group
• n R 1 are independently a hydroxy group, a halogen atom, a carboxy group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group
• the number of optionally substituted carbon atoms represents a group selected from the group consisting of alkyl groups of 1 to 10 and optionally substituted alkoxy groups having 1 to 10 carbon atoms
• n represents an integer of 0 to 5
• * represents the reaction product
• a resist underlayer film characterized by being a baked product of a coating film comprising the resist underlayer film-forming composition according to any one of [1] to [7].
• a step of forming a resist underlayer film comprising the resist underlayer film-forming composition according to any one of [1] to [7] on a semiconductor substrate; forming a resist film on the resist underlayer film; a step of forming a resist pattern by irradiating the resist film with light or an electron beam and then developing; forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern; a step of processing a semiconductor substrate with the patterned resist underlayer film;
• a method of manufacturing a semiconductor device comprising:
• the composition for forming a resist underlayer film of the present invention has excellent applicability to a semiconductor substrate to be processed by including a naphthalene ring unit in the polymer, and adhesion between the resist and the resist underlayer film interface during resist pattern formation.
• a naphthalene ring unit in the polymer By being excellent in resist pattern peeling, deterioration of LWR (Line Width Roughness, Line Width Roughness, Line Width Fluctuation (roughness)) during resist pattern formation can be suppressed, and the resist pattern size (minimum CD size) can be minimized, and a favorable resist pattern having a rectangular shape can be formed.
• EUV wavelength 13.5 nm
• EB electron beam
• the resist underlayer film-forming composition of the present invention has the following formula (100): (In formula (100), Ar 1 and Ar 2 each independently represent an optionally substituted aromatic ring having 6 to 40 carbon atoms, and at least one of Ar 1 and Ar 2 is a naphthalene ring; , L 1 represents a single bond, an optionally substituted alkylene group having 1 to 10 carbon atoms or an optionally substituted alkenylene group having 2 to 10 carbon atoms, and T 1 and T 2 are each independently represents a single bond, an ester bond or an ether bond, and E represents an epoxy group.) with a compound (B) containing at least two groups reactive with an epoxy group. Includes products and solvents.
• the compound (A) and the compound (B) are reacted, for example, by a known method described in Examples to obtain a reaction product (polymer, polymer) of the compound (A) and the compound (B). can be manufactured.
• the aromatic rings having 6 to 40 carbon atoms include benzene, naphthalene, anthracene, acenaphthene, fluorene, triphenylene, phenalene, phenanthrene, indene, indane, indacene, pyrene, chrysene, perylene, naphthacene, pentacene, coronene, heptacene, benzo [a]anthracene, dibenzophenanthrene and dibenzo[a,j]anthracene.
• alkylene group having 1 to 10 carbon atoms examples include methylene group, ethylene group, n-propylene group, isopropylene group, cyclopropylene group, n-butylene group, isobutylene group, s-butylene group, t-butylene group, cyclobutylene group, 1-methyl-cyclopropylene group, 2-methyl-cyclopropylene group, n-pentylene group, 1-methyl-n-butylene group, 2-methyl-n-butylene group, 3-methyl-n-butylene group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene group, 1-ethyl-n-propylene group, cyclopentylene group, 1- methyl-cyclobutylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-di
• Examples of the alkenylene group having 2 to 10 carbon atoms include groups having at least one double bond obtained by removing a hydrogen atom from each adjacent carbon atom among the alkylene groups having 2 to 10 carbon atoms.
• a vinylene group is preferred.
• the "may be substituted” means that some or all of the hydrogen atoms present in the alkylene group having 1 to 10 carbon atoms or the alkenylene group having 2 to 10 carbon atoms are, for example, a hydroxy group, a halogen optionally substituted by an atom, a carboxyl group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms means that
• alkyl group having 1 to 10 carbon atoms examples include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t- butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n -butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1 -methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group
• alkoxy group having 1 to 10 carbon atoms examples include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n -pentoxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n- propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3 -methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group group, 2,2-
• the compound (A) a commercially available compound having at least two epoxy groups containing a naphthalene structure and having the effect of the present invention may be used. Specific examples are EPICLON HP-4770, HP-6000, WR-600 (all manufactured by DIC Corporation).
• R 3 represents a hydrogen atom or a methyl group
• Ar each independently represents a naphthylene group, a phenylene group, or a naphthylene group having an alkyl group having 1 to 4 carbon atoms or a phenyl group as a substituent.
• each R 2 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• n and m are each an integer of 0 to 2
• R 1 represents a hydrogen atom or an epoxy group-containing aromatic hydrocarbon group represented by the following general formula (3-2), provided that the total number of aromatic nuclei in the formula is 2 to 8.
• the bonding position to the naphthalene skeleton may be either of the two rings constituting the naphthalene ring.
• R 3 represents a hydrogen atom or a methyl group
• each Ar is independently a naphthylene group, a phenylene group, an alkyl group having 1 to 4 carbon atoms, or a phenyl group as a substituent.
• the compound represented by the above formula (100) and the above general formula (3) is added to the solid content of the resist underlayer film-forming composition of the present invention, for example, 10% by mass or more, 30% by mass or more, 50% by mass or more. may contain.
• the compound (B) may contain a heterocyclic structure or an aromatic ring structure having 6 to 40 carbon atoms.
• the heterocyclic structures include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thianthrene, phenothiazine, phenoxazine, Xanthenes, acridines, phenazines, carbazoles, triazinediones, triazinediones and triazinetriones.
• heterocyclic structure may be a structure derived from barbituric acid.
• the aromatic ring structure having 6 to 40 carbon atoms is as described above.
• the compound (B) has the following formula (101): (In formula (101), X 1 is the following formula (2), formula (3), formula (4), or formula (0): (In formulas (2), (3), (4) and (0), R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 10 alkenyl group, benzyl group or phenyl group, and said alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, benzyl group and phenyl group are those having 1 to 6 carbon atoms.
• R 1 and R 2 may be bonded together to form a ring having 3 to 10 carbon atoms, and R 3 is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 2 1 to 10 alkenyl group, benzyl group or phenyl group, and the phenyl group is an alkyl group having 1 to 10 carbon atoms, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a nitro group, a cyano group, a hydroxy and a group selected from the group consisting of an alkylthio group having 1 to 10 carbon atoms.)).
• the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• alkylthio groups having 1 to 10 carbon atoms examples include methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio and decanylthio groups.
• the above-mentioned rings having 3 to 10 carbon atoms include cyclopropane, cyclobutane, cyclopentane, cyclopentadiene, cyclohexane, cycloheptane, cyclooctane, cyclononane and cyclodecane.
• the meaning of each other term is as described above.
• the terminal of the reaction product is represented by the following formula (102):
• Ar represents an optionally substituted aromatic ring having 6 to 40 carbon atoms
• L 1 is an ester bond, an ether bond or an optionally substituted alkenylene having 2 to 10 carbon atoms group
• n R 1 are independently a hydroxy group, a halogen atom, a carboxy group, a nitro group, a cyano group, a methylenedioxy group, an acetoxy group, a methylthio group, an amino group
• the number of optionally substituted carbon atoms represents a group selected from the group consisting of alkyl groups of 1 to 10 and optionally substituted alkoxy groups having 1 to 10 carbon atoms
• n represents an integer of 0 to 5
• * represents the reaction product represents a binding portion.
• the structure represented by the formula (1-2) may be derived from cinnamic acid or salicylic acid optionally substituted with a halogen atom.
• Compounds capable of binding to the terminals of the reaction product for deriving the structure represented by formula (1-2) include compounds represented by the following formulas.
• the end of the reaction product may have an aliphatic ring structure in which the carbon-carbon bond may be interrupted by a heteroatom and may be substituted with a substituent, as described in WO2020/226141.
• the aliphatic ring may be a monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms.
• the polycyclic aliphatic ring may be a bicyclo ring or a tricyclo ring.
• the aliphatic ring may have at least one unsaturated bond.
• the substituent of the aliphatic ring is a hydroxy group, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, and may be selected from carboxy groups;
• the terminal of the reaction product may have a structure represented by the following formula (1) described in WO2012/124597.
• R 1 , R 2 and R 3 each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 13 carbon atoms or a hydroxy group, and the R 1 , R 2 and At least one of R 3 is the above hydrocarbon group, m and n each independently represent 0 or 1, the main chain of the polymer is bonded to a methylene group when n represents 1, and n represents 0 In the case it bonds with the group represented by -O-.
• the terminal of the reaction product may have a structure represented by the following formula (1a), (1b) or (2) described in WO2013/168610.
• R 1 represents a hydrogen atom or a methyl group
• R 2 and R 3 each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 6 carbon atoms, or an alicyclic hydrocarbon group.
• R 4 represents a hydrogen atom or a hydroxy group
• Q 1 represents an arylene group
• v represents 0 or 1
• y represents an integer of 1 to 4
• w represents an integer of 1 to 4
• x 1 represents 0 or 1
• x 2 represents an integer of 1 to 5.
• the terminal of the reaction product may have a structure represented by the following formula (1) described in WO2015/046149.
• R 1 , R 2 and R 3 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 13 carbon atoms, a halogeno group or a hydroxy group; At least one of 2 and R 3 represents the above alkyl group, Ar represents a benzene ring, naphthalene ring or anthracene ring, and two carbonyl groups are respectively bonded to two adjacent carbon atoms of the ring represented by Ar. and X represents a linear or branched alkyl group having 1 to 6 carbon atoms which may have an alkoxy group having 1 to 3 carbon atoms as a substituent.
• the end of the reaction product may have a structure represented by the following formula (1) or (2) described in WO2015/163195 at the end of the polymer chain.
• R 1 represents an optionally substituted alkyl group having 1 to 6 carbon atoms, phenyl group, pyridyl group, halogeno group or hydroxy group
• R 2 represents a hydrogen atom
• 6 alkyl group, hydroxy group, halogeno group or an ester group represented by -C( O)O-X
• X represents an optionally substituted alkyl group having 1 to 6 carbon atoms
• R 3 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group or a halogeno group
• R 4 represents a direct bond or a divalent organic group having 1 to 8 carbon atoms
• R 5 represents represents a divalent organic group having 1 to 8 carbon atoms
• A represents an aromatic ring or an aromatic heterocycle
• t represents 0 or 1
• the terminal of the reaction product may have a structure represented by the following formula (1) or (2) described in WO2020/071361.
• X is a divalent organic group
• A is an aryl group having 6 to 40 carbon atoms
• R 1 is a halogen atom, and an alkyl group or an alkoxy group having 1 to 10 carbon atoms
• R 2 and R 3 are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted an aryl group having 6 to 40 carbon atoms
• n1 and n3 are each independently an integer of 1 to 12
• n2 is an integer of 0 to 11.
• the lower limit of the weight-average molecular weight of the reaction product (polymer) measured by gel permeation chromatography, for example, described in the Examples, is, for example, 1,000 or 2,000, and the weight-average molecular weight of the reaction product is, for example, 30,000, 20,000, or 10,000.
• the resist underlayer film-forming composition of the present invention may be an EUV resist underlayer film-forming composition used in an EUV (extreme ultraviolet) exposure process.
• the solvent used in the composition for forming a resist underlayer film of the present invention is not particularly limited as long as it is a solvent capable of uniformly dissolving the components such as the above polymers that are solid at room temperature.
• the organic solvents used are preferred.
• 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 ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxyprop
• 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.
• thermal acid generators include, for example, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid ( p-phenolsulfonic acid pyridinium salt), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid
• Examples of the photoacid generator include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.
• Onium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octane sulfonate, diphenyliodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium camphorsulfonate.
• iodonium salt compounds such as bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate sulfonium salt compounds such as
• sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-normalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide and N-(trifluoromethanesulfonyloxy)naphthalimide. 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-toluenesulfonyl diazomethane.
• the acid generator can be used alone or in combination of two or more.
• the content of the acid generator is, for example, 0.1% by mass to 50% by mass, preferably 1% by mass to 30% by mass, relative to the following cross-linking agent. .
• cross-linking agents contained as optional components in the resist underlayer film-forming composition of the present invention include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (tetramethoxy methyl glycoluril) (POWDERLINK® 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(butoxymethyl)urea and 1,1,3,3-tetrakis(methoxymethyl)urea.
• cross-linking agent of the present application is a nitrogen-containing compound having 2 to 6 substituents per molecule represented by the following formula (1d) that binds to a nitrogen atom, as described in International Publication No. 2017/187969. There may be.
• R 1 represents a methyl group or an ethyl group.
• 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 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.
• Examples of the glycoluril derivative represented by the formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).
• the nitrogen-containing compound having 2 to 6 substituents represented by the formula (1d) in one molecule has 2 to 6 substituents in the molecule represented by the following formula (2d) bonded to the nitrogen atom. 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 an ethyl group
• R 4 represents an alkyl group having 1 to 4 carbon atoms.
• the glycoluril derivative represented by the formula (1E) is obtained by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the formula (3d).
• a nitrogen-containing compound having 2 to 6 substituents represented by the above 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
• R 4 each independently represent an alkyl group having 1 to 4 carbon atoms. represents.
• Examples of the glycoluril derivative represented by the formula (2E) include compounds represented by the following formulas (2E-1) to (2E-4).
• examples of the compound represented by the formula (3d) include compounds represented by the following formulas (3d-1) and (3d-2).
• cross-linking agent may be a cross-linkable compound represented by the following formula (G-1) or formula (G-2) described in International Publication 2014/208542.
• Q 1 represents a single bond or a monovalent organic group
• R 1 and R 4 each represent an alkyl group having 2 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
• 2 to 10 alkyl group 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 a 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 3 ⁇ (n1+n2+n3+n4) ⁇ 6.
• n5 is an integer satisfying 1 ⁇ n5 ⁇ 3, n6 is an integer satisfying 1 ⁇ n6 ⁇ 4, n7 is an integer satisfying 0 ⁇ n7 ⁇ 3, n8 is an integer satisfying 0 ⁇ n8 ⁇ 3, and 2 ⁇ (n5+n6+n7+n8) ⁇ 5 show.
• m1 represents an integer from 2 to 10; )
• the crosslinkable compound represented by the above formula (G-1) or formula (G-2) comprises a compound represented by the following formula (G-3) or formula (G-4) and a hydroxyl group-containing ether compound or carbon atom It may be obtained by reaction with alcohols of numbers 2 to 10.
• 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.
• 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 3 ⁇ (n9+n10+n11+n12) ⁇ 6. show.
• 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; )
• Me represents a methyl group.
• the content of the cross-linking agent is, for example, 1% by mass to 50% by mass, preferably 5% by mass to 30% by mass, relative to the reaction product.
• a surfactant may be further added to the resist underlayer film-forming composition of the present invention in order to prevent pinholes, striations, and the like from occurring and to further improve coatability against surface unevenness.
• surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and polyoxyethylene nonylphenol ether.
• Polyoxyethylene alkyl allyl ethers such as polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc.
• sorbitan fatty acid esters polyoxyethylene sorbitan such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate
• Nonionic surfactants such as fatty acid esters, F-top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade names), Megafac F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd., commercial products name), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade name), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., trade name), etc.
• organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
• the blending amount of these surfactants is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on the total solid content of the resist underlayer film-forming composition of the present invention.
• These surfactants may be added singly or in combination of two or more.
• the solid content contained in the resist underlayer film-forming composition of the present invention is, for example, 0.01% by mass to 10% by mass.
• the resist underlayer film according to the present invention can be produced by applying the resist underlayer film-forming composition described above onto a semiconductor substrate and baking the composition.
• Semiconductor substrates to which the resist underlayer film-forming composition of the present invention is applied include, for example, silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride. be done.
• the inorganic film is formed by, for example, an ALD (atomic layer deposition) method, a CVD (chemical vapor deposition) method, a reactive sputtering method, an ion plating method, or a vacuum deposition method. It is formed by a spin coating method (spin on glass: SOG).
• the inorganic film examples 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 oxynitride film, a tungsten film, a gallium nitride film, and a gallium arsenide film. is mentioned.
• the resist underlayer film-forming composition of the present invention is applied onto such a semiconductor substrate by a suitable coating method such as a spinner or coater. Thereafter, a resist underlayer film is formed by baking using a heating means such as a hot plate. 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. Preferably, the baking temperature is 120° C. to 350° C. and the baking time is 0.5 minutes to 30 minutes, and more preferably the baking temperature is 150° C. to 300° C. and the baking time is 0.8 minutes to 10 minutes.
• the film thickness of the resist underlayer film to be formed 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).
• a method of manufacturing a patterned substrate includes the following steps. Usually, it is manufactured by forming a photoresist layer on a resist underlayer film.
• the photoresist formed by coating and baking on the resist underlayer film by a method known per se is not particularly limited as long as it is sensitive to the light used for exposure. Both negative and positive photoresists can be used.
• positive photoresist composed of novolac resin and 1,2-naphthoquinonediazide sulfonic acid ester;
• a chemically amplified photoresist comprising a low-molecular compound that decomposes to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, and a binder having a group that decomposes with an acid to increase the alkali dissolution rate.
• Examples thereof include V146G (trade name) manufactured by JSR Corporation, APEX-E (trade name) manufactured by Shipley, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., AR2772 (trade name) and SEPR430 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Also, for example, Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).
• resist compositions include the following compositions.
• Actinic ray-sensitive or sensitive resin containing a resin A having a repeating unit having an acid-decomposable group in which the polar group is protected by a protective group that is released by the action of an acid, and a compound represented by the general formula (21) A radioactive resin composition.
• m represents an integer of 1-6.
• 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 optionally substituted alkylene group or a single bond.
• W1 represents an optionally substituted cyclic organic group.
• M + represents a cation
• a radiation-sensitive resin 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-labile group, and an acid generator. Composition.
• Ar is a group obtained by removing (n+1) hydrogen atoms from arene having 6 to 20 carbon atoms.
• R 1 is a hydroxy group, a sulfanyl group, or a monovalent group having 1 to 20 carbon atoms.
• n is an integer of 0 to 11.
• 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 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 groups selected from the group consisting of a hydroxy group and a carboxyl group represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have ]
• resist films examples 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
• Each R 3 is 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, an ester bond, a lactone ring, or a phenylene is a linking group having 1 to 12 carbon atoms and containing at least one selected from a group and a naphthylene group
• X 2 is a single bond, an ester bond or an 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 carbon atoms or an arylene group having 6 to 10 carbon atoms, and 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,
• 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 group having 1 to 12 carbon atoms.
• Rf 1 to Rf 4 independently represents a hydrogen atom, a fluorine atom or a trifluoro a methyl group, at least one of which is a fluorine atom or a trifluoromethyl group, and Rf 1 and Rf 2 may combine to form a carbonyl group
• R 1 to R 5 each independently linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, linear, branched or cyclic alkenyl groups having 2 to 12 carbon atoms, alkynyl groups having 2 to 12 carbon atoms, and 6 to 20 carbon atoms an aryl group, 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 hydrogen atoms of these groups are hydroxy groups, carboxy groups,
• 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 C 1 to 6 alkyl groups or halogen atoms other than bromine,
• X 1 is a single bond or a phenylene group, or a linear, branched or cyclic C 1-12 group which may contain an ester group or a lactone ring is an alkylene group of X 2 is -O-, -O-CH 2 - or -NH-,
• m is an integer of 1 to 4, and
• n is an integer of 0 to 3.
• a resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, Containing a base component (A) whose solubility in a developer changes under the action of an acid and a fluorine additive component (F) which exhibits decomposability in an alkaline developer,
• each Rf 21 is independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group, or a cyano group.
• n" is an integer of 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).
• each R is 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-labile site.
• a aryl is an optionally substituted divalent aromatic cyclic group.
• 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.
• An inorganic oxo/hydroxo-based composition An inorganic oxo/hydroxo-based composition.
• 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, wherein the solution from about 0.0025M to about 1.5M tin, and R is an alkyl or cycloalkyl group having 3 to 31 carbon atoms, wherein said alkyl or cycloalkyl group is a secondary or secondary A coating solution bonded to tin at a tertiary carbon atom.
• RSnO (3/2-x/2) (OH) x where 0 ⁇ x ⁇ 3, wherein the solution from about 0.0025M to about 1.5M tin, and R is an alkyl or cycloalkyl group having 3 to 31 carbon atoms, wherein said alkyl or cycloalkyl group is a secondary or secondary A coating solution bonded to tin at a tertiary carbon atom.
• An aqueous inorganic pattern-forming precursor comprising a mixture of water, a metal suboxide cation, a polyatomic inorganic anion, and a radiation-sensitive ligand comprising a peroxide group.
• Exposure is performed through a mask (reticle) for forming a predetermined pattern, and for example, i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet) or EB (electron beam) is used. is preferably applied for EB (electron beam) or EUV (extreme ultraviolet) exposure, and preferably for EUV (extreme ultraviolet) exposure.
• An alkaline developer is used for development, and the development temperature is selected from 5° C. to 50° C. and the development time is appropriately selected from 10 seconds to 300 seconds.
• alkaline developer examples include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, 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; Aqueous solutions of alkalis such as quaternary ammonium salts, pyrrole, cyclic amines such as piperidine, and the like can be used.
• inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, secondary amines such as di-n-butyl
• an alcohol such as isopropyl alcohol or a nonionic surfactant may be added in an appropriate amount to the aqueous alkali solution.
• Preferred developers among these are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline.
• a surfactant or the like can be added to these developers. It is also possible to use a method of developing with an organic solvent such as butyl acetate instead of the alkaline developer, and developing the portion where the rate of alkali dissolution of the photoresist is not improved.
• the resist underlayer film is dry-etched.
• the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed, and when the inorganic film is not formed on the surface of the semiconductor substrate used, the semiconductor substrate is exposed. expose the surface.
• the substrate is processed by a method known per se (dry etching method, etc.), and a semiconductor device can be manufactured.
• the weight average molecular weights of the polymers shown in Synthesis Examples 1 to 10 and Comparative Synthesis Example 1 below in this specification are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC).
• GPC gel permeation chromatography
• GPC column TSKgel Super-MultiporeHZ-N (2 columns) Column temperature: 40°C Solvent: Tetrahydrofuran (THF) Flow rate: 0.35 ml/min Standard sample: Polystyrene (manufactured by Tosoh Corporation)
• polymer 1 had a weight average molecular weight of 3,200 and a polydispersity of 3.7 in terms of standard polystyrene.
• the structure present in polymer 1 is shown in the formula below.
• reaction was carried out at 140° C. for 24 hours to obtain a solution containing polymer 2.
• GPC analysis revealed that the obtained polymer 2 had a weight average molecular weight of 4,900 and a polydispersity of 3.5 in terms of standard polystyrene.
• polymer 3 had a weight average molecular weight of 3,400 and a polydispersity of 3.2 in terms of standard polystyrene.
• the structure present in polymer 3 is shown in the formula below.
• polymer 4 had a weight average molecular weight of 4,000 and a polydispersity of 3.4 in terms of standard polystyrene.
• the structure present in polymer 4 is shown in the formula below.
• polymer 5 had a weight average molecular weight of 4,300 and a polydispersity of 3.4 in terms of standard polystyrene.
• the structure present in polymer 5 is shown in the formula below.
• reaction was carried out at 140° C. for 24 hours to obtain a solution containing polymer 6.
• GPC analysis revealed that the obtained polymer 6 had a weight average molecular weight of 4,500 and a polydispersity of 2.8 in terms of standard polystyrene.
• reaction was carried out at 140° C. for 24 hours to obtain a solution containing polymer 7.
• GPC analysis revealed that the obtained polymer 7 had a weight average molecular weight of 4,500 and a polydispersity of 2.8 in terms of standard polystyrene.
• reaction was carried out at 140° C. for 24 hours to obtain a solution containing polymer 8.
• GPC analysis revealed that the obtained polymer 8 had a weight average molecular weight of 3,700 and a polydispersity of 2.6 in terms of standard polystyrene.
• reaction was carried out at 140° C. for 24 hours to obtain a solution containing polymer 10.
• GPC analysis revealed that the obtained polymer 10 had a weight average molecular weight of 6,300 and a polydispersity of 2.9 in terms of standard polystyrene.
• Comparative Synthesis Example 1 100.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Kasei Co., Ltd.), 66.4 g of 5,5-diethylbarbituric acid (manufactured by Tateyama Kasei Co., Ltd.), and 4.1 g of benzyltriethylammonium chloride were placed in a reaction vessel. It was dissolved in 682.00 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, reaction was carried out at 130° C. for 24 hours to obtain a solution containing Comparative Polymer 1. GPC analysis revealed that the obtained comparative polymer 1 had a weight average molecular weight of 6,800 and a polydispersity of 4.8 in terms of standard polystyrene. The structure present in Comparative Polymer 1 is shown in the formula below.
• tetramethoxymethylglycoluril is PL-LI
• Imidazo[4,5-d]imidazole-2,5(1H,3H)-dione tetrahydro-1,3,4,6-tetrakis[ (2-methoxy-1-methylethoxy)methyl]-
• PGME-PL pyridinium-p-hydroxybenzenesulfonic acid
• surfactant is R-30N
• propylene glycol monomethyl ether acetate is PGMEA
• propylene glycol monomethyl ether is PGME abbreviated.
• Each addition amount is shown in parts by mass.
• a photoresist developer for 60 seconds, cooled to room temperature on a cooling plate, and a 2.38% tetramethylammonium hydroxide aqueous solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., commercial product) is used as a photoresist developer. Puddle development was performed for 30 seconds using NMD-3). A resist pattern with a line size of 16 nm to 28 nm was formed. A scanning electron microscope (CG4100, manufactured by Hitachi High-Technologies Corporation) was used for the length measurement of the resist pattern.
• CG4100 manufactured by Hitachi High-Technologies Corporation
• the composition for forming a resist underlayer film according to the present invention is a composition for forming a resist underlayer film capable of forming a desired resist pattern, a method for producing a substrate with a resist pattern using the composition for forming a resist underlayer film, a semiconductor A method of manufacturing a device can be provided.

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