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
  • G03F7/20—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
• • 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
• • 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 resist underlayer film-forming composition that can be used in lithography processes in semiconductor manufacturing, particularly in cutting-edge (ArF, EUV, EB, etc.) lithography processes.
• the present invention also relates to a method for manufacturing a semiconductor substrate with a resist pattern to which a resist underlayer film obtained from the composition for forming a resist underlayer film is applied, and a method for 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 photoresist pattern on the substrate surface.
• Patent Document 1 discloses an underlayer film-forming composition for lithography containing a naphthalene ring having a halogen atom.
• Patent Document 2 discloses a halogenated antireflection coating.
• Patent Document 3 discloses a composition for forming a resist underlayer film.
• 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), and a faster dry etching rate than the resist film. mentioned.
• 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.
• the present invention provides a resist underlayer film-forming composition for forming a resist underlayer film capable of forming a desired resist pattern, a resist underlayer film obtained from the resist underlayer film-forming composition, and patterning using the resist underlayer film. It is an object of the present invention to provide a method for manufacturing a semiconductor substrate having a resist film formed thereon and a method for manufacturing a semiconductor device.
• a resist underlayer film-forming composition containing a compound represented by the following formula (1) and a solvent.
• each X independently represents a halogen atom or a monovalent organic group having at least one halogen atom.
• Y represents an n-valent group.
• n is 2 to 6 represents an integer of [2]
• X 1 represents a monovalent hydrocarbon group having at least one halogen atom.
• X 2 is —O—CO— *1 (*1 is a bond with X 1 .
• a method of manufacturing a semiconductor substrate having a patterned resist film comprising: [14] forming, on a semiconductor substrate, a resist underlayer film comprising the resist underlayer film-forming composition according to any one of [1] to [11]; forming a resist film on the resist underlayer film; 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
• a resist underlayer film-forming composition for forming a resist underlayer film capable of forming a desired resist pattern, a resist underlayer film obtained from the resist underlayer film-forming composition, and a composition using the resist underlayer film , a method for manufacturing a semiconductor substrate having a patterned resist film, and a method for manufacturing a semiconductor device.
• the resist underlayer film-forming composition of the present invention contains a compound represented by the following formula (1) and a solvent.
• the resist underlayer film-forming composition may contain other components such as a cross-linking agent and an acid generator.
• each X independently represents a halogen atom or a monovalent organic group having at least one halogen atom.
• Y represents an n-valent group.
• n is 2 to 6 represents an integer of
• the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom or an iodine atom.
• the halogen atom in the compound represented by formula (1) may be one type or a plurality of types. is preferable because it is easy to
• n is preferably an integer of 2-5, more preferably an integer of 3-4.
• the number of carbon atoms in the monovalent organic group of X is not particularly limited, but is preferably 1-50, more preferably 1-30, and particularly preferably 3-20.
• the number of halogen atoms that X has is not particularly limited, and may be 1 or 2 or more, preferably 1 to 5, more preferably 1 to 3.
• a plurality of X's may be the same or different, but are preferably the same from the viewpoint of facilitating the production of the compound represented by formula (1).
• X may or may not have an aromatic hydrocarbon ring.
• aromatic hydrocarbon rings include benzene ring, naphthalene ring, and anthracene ring.
• At least one of the halogen atoms of X is preferably bonded to a carbon atom that is not a carbon atom constituting an aromatic hydrocarbon ring.
• Such carbon atoms include, for example, carbon atoms that constitute an alkyl group.
• X is preferably represented by the following formula (2).
• X 1 represents a monovalent hydrocarbon group having at least one halogen atom.
• X 2 is —O—CO— *1 (*1 is a bond with X 1 . represents.), -NR- (R represents a monovalent organic group having 1 to 12 carbon atoms.), or -S-.* represents a bond.)
• the number of carbon atoms in the hydrocarbon group of X 1 is not particularly limited, but is preferably 1-20, more preferably 1-12, and particularly preferably 1-6.
• the hydrocarbon group for X 1 includes, for example, an aromatic hydrocarbon group and a non-aromatic hydrocarbon group.
• X 1 is preferably an alkyl group having 1 to 12 carbon atoms and having at least one halogen atom, more preferably an alkyl group having 1 to 6 carbon atoms and having at least one halogen atom.
• the alkyl group having 1 to 12 carbon atoms and having at least one halogen atom is, in other words, an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted with a halogen atom, and It is also referred to as a halogenated alkyl group of ⁇ 12.
• halogenated alkyl groups include, when the halogen atom is a fluorine atom, trifluoromethyl group, 2,2,2-trifluoroethyl group, perfluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, per fluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, per fluorobutyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, perfluoro pentyl group, 2,2,3,3,4,4,5,5,6,
• halogenated alkyl group when the halogen atom is a chlorine atom, for example, a monochloromethyl group, 1-chloroethyl group, 2-chloroethyl group, 2-chloroisobutyl group, 1,2-dichloroethyl group, 1,3 -dichloroisopropyl group, 2,3-dichloro-t-butyl group, 1,2,3-trichloropropyl group and the like.
• halogenated alkyl group when the halogen atom is a bromine atom, for example, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group, 1,2-dibromoethyl group, 1,3- Dibromoisopropyl group, 2,3-dibromo-t-butyl group, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl and the like.
• halogenated alkyl group when the halogen atom is an iodine atom, for example, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 1,3-di iodoisopropyl group, 2,3-diiodo-t-butyl group, 1,2,3-triiodopropyl group and the like.
• iodine atom for example, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 1,3-di iodoisopropyl group, 2,3-diiodo-t-butyl group, 1,2,3-triiodopropyl group and the like.
• X 2 is preferably —O—CO— *1 (*1 represents a bond with X 1) because the compound represented by formula ( 1 ) can be easily produced.
• R of -NR- is not particularly limited as long as it is a monovalent organic group having 1 to 12 carbon atoms, for example, a hydrocarbon group having 1 to 12 carbon atoms, a carbon having at least one halogen atom
• Examples include hydrocarbon groups having 1 to 12 atoms.
• Hydrocarbon groups include, for example, alkyl groups. Specific examples of the alkyl group having 1 to 12 carbon atoms and having at least one halogen atom are the same as above.
• R is, for example, the same as X 1 which together constitute *-X 2 -X 1 .
• Y is not particularly limited as long as it is an n-valent group, but the number of constituent atoms of Y is, for example, 5-30.
• Y has, for example, a carbon atom and at least one of a nitrogen atom and an oxygen atom.
• Y is preferably represented by the following formula (11), (12) or (13), more preferably represented by formula (11) or (12).
• R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• R 2 represents a single bond or 1 carbon atom. represents an alkylene group of ⁇ 3.
• n in formula (1) is usually 3.
• n in formula (1) is 4.
• n in formula (1) is usually 3.
• R 1 and R 2 examples include a combination in which R 1 is a hydrogen atom and R 2 is a single bond, a combination in which R 1 is an ethyl group and R 2 is a methylene group, and the like.
• the compound represented by formula (1) may be of one type or two or more types.
• a mixture of two or more types of compounds represented by formula (1) may be obtained. Any mixture can be used.
• the molecular weight of the compound represented by formula (1) is not particularly limited, it is preferably 200 to 2,000, more preferably 300 to 1,500, and particularly preferably 500 to 1,300.
• the method for producing the compound represented by the formula (1) is not particularly limited, but for example, a production method of reacting a compound represented by the following formula (1A) with a compound represented by the following formula (1B). mentioned.
• the compound represented by formula (1A) may be a manufactured product or a commercially available product.
• Commercially available products include, for example, triglycidyl isocyanurate (manufactured by Nissan Chemical Industries, Ltd.), 1,3,4,6-tetraglycidyl glycoluril (manufactured by Shikoku Kasei Co., Ltd.), Denacol EX-614B (sorbitol polyglycidyl ether, Nagase Chemtex company), Denacol EX-313 (glycerol polyglycidyl ether, manufactured by Nagase ChemteX), Denacol EX-512 (polyglycerol polyglycidyl ether, manufactured by Nagase ChemteX), Denacol EX-321 (trimethylolpropane polyglycidyl ether) , manufactured by Nagase ChemteX Corporation), Denacol EX-321L (trimethylolpropane polyglycidyl
• reaction form of the method for producing the compound represented by formula (1) is an addition reaction between a glycidyl group and a carboxyl group.
• a quaternary ammonium salt, a phosphonium salt, or the like may be used as a catalyst.
• quaternary ammonium salts include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogensulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, N,N-dimethyl-N - benzylanilinium hexafluoroantimonate, N,N-dimethyl-N-benzylanilinium tetrafluoroborate, N,N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N,N-diethyl-N-benzyltrifluoromethane sulfonate, N,N-dimethyl-N-(4-methoxybenzyl)pyridinium hexafluoroantimonate,
• Phosphonium salts include, for example, triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium bromide, triphenylbenzylphosphonium iodide, triethylbenzylphosphonium chloride, tetrabutylphosphonium bromide and the like.
• the amount of catalyst used is not particularly limited.
• the method for producing the compound represented by formula (1) may be carried out in the presence of an organic solvent or in the absence of a solvent.
• organic solvent to be used include ethers, alkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, esters, ketones and the like.
• Ethers include, for example, diethyl ether, tetrahydrofuran, tetrahydropyran, diisopropyl ether, diphenyl ether, anisole, phenetol, guaiacol; alkylene glycols: ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol and the like.
• Alkylene glycol monoalkyl ethers include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono and ethyl ether.
• alkylene glycol dialkyl ethers examples include ethylene glycol dimethyl ether (DME), ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, butylene glycol dimethyl ether, butylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether.
• DME ethylene glycol dimethyl ether
• DME ethylene glycol diethyl ether
• propylene glycol dimethyl ether propylene glycol dimethyl ether
• propylene glycol diethyl ether propylene glycol diethyl ether
• butylene glycol dimethyl ether butylene glycol diethyl ether
• diethylene glycol dimethyl ether examples include ethylene glycol diethyl ether.
• esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl formate, ethyl formate, propyl formate, butyl formate, and methyl benzoate.
• ketones include acetone, acetylacetone, methyl ethyl ketone, cyclohexanone, cyclopentanone and the like.
• the reaction temperature in the method for producing the compound represented by formula (1) is not particularly limited, but examples thereof include 20°C to 60°C.
• the reaction time in the method for producing the compound represented by formula (1) is not particularly limited, but includes, for example, 1 hour to 72 hours.
• a single compound represented by formula (1) may be obtained, or a mixture of two or more compounds represented by formula (1) may be obtained, or a mixture of one or more compounds represented by formula (1) and other compounds may be obtained.
• the product obtained by the method for producing the compound represented by formula (1) is a mixture
• the mixture may be purified and used for the preparation of the resist underlayer film-forming composition, or the mixture may be used without purification. You may use for preparation of a resist underlayer film forming composition.
• the content of the compound represented by the formula (1) in the resist underlayer film-forming composition is not particularly limited, but from the viewpoint of solubility, it is 0.1% by mass relative to the entire resist underlayer film-forming composition. ⁇ 50% by mass is preferable, and 0.1% by mass to 10% by mass is more preferable.
• the solvent used in the resist underlayer film-forming composition is not particularly limited as long as it can uniformly dissolve the components that are solid at room temperature, but 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-hydroxyisobuty
• 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.
• cross-linking agent contained as an optional component in the resist underlayer film-forming composition has a functional group that reacts with the secondary hydroxyl group of the compound represented by the formula (1).
• cross-linking agents 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 (butoxymethyl)urea and 1,1,3,3-tetrakis(methoxymethyl)urea.
• the cross-linking agent is a nitrogen-containing compound having 2 to 6 substituents in one molecule represented by the following formula (1d) that binds to a nitrogen atom, as described in WO 2017/187969. good too.
• R 1 represents a methyl group or an ethyl group. * represents a bond that bonds 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 1s each independently represent a methyl group or an ethyl group
• R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.
• glycoluril derivative represented by the formula (1E) examples 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
• * represents a bond bonding to a nitrogen atom.
• 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, and R 4 each independently represent an alkyl group having 1 to 4 carbon atoms. represents.
• 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 formulas (3d-1) and (3d-2).
• 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 compound represented by the formula (1). %.
• thermal acid generator Either a thermal acid generator or a photoacid generator can be used as the acid generator contained as an optional component in the composition for forming a resist underlayer film, but it is preferable to use a thermal acid generator.
• the thermal acid generator include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid.
• Examples of the photoacid generator include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.
• Onium salt compounds include, for example, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octane sulfonate, diphenyliodonium camphorsulfonate, and bis(4-tert-butylphenyl).
• Iodonium salt compounds such as iodonium camphorsulfonate and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium and sulfonium salt compounds such as trifluoromethanesulfonate.
• 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 cross-linking agent. .
• a surfactant may be further added to the composition for forming a resist underlayer film in order to further improve coatability against surface unevenness without generating pinholes, striations, and the like.
• 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.
• These surfactants may be added singly or in combination of two or more.
• the non-volatile content contained in the resist underlayer film-forming composition 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.
• a resist underlayer film is a baked product of a coating film made of a resist underlayer film-forming 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 semiconductor substrate having a patterned resist film includes at least the following steps.
• a method of manufacturing a semiconductor device includes at least the following steps. - A step of forming a resist underlayer film comprising the resist underlayer film-forming composition of the present invention on a semiconductor substrate. - A step of forming a resist film on the resist underlayer film. - Irradiating the resist film with light or an electron beam, followed by A step of forming a resist pattern by development A step of forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern; ⁇ The process of processing a semiconductor substrate with a patterned resist underlayer film
• a method for manufacturing a semiconductor substrate having a patterned resist film and a method for manufacturing a semiconductor device include, for example, 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 known method 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.
• 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
• u is an integer of 0 to 3, provided that , m+u are integers from 1 to 4.
• the fluorine additive component (F) includes 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): fluorine A resist composition containing a resin component (F1).
• 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.
• the resist underlayer film-forming composition of the invention is preferably applied for EB (electron beam) or EUV (extreme ultraviolet) exposure, and more 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 are aqueous solutions of quaternary ammonium salts, more preferably aqueous solutions of tetramethylammonium hydroxide and aqueous solutions of 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 semiconductor substrate is processed by a known method (dry etching method, etc.), and a semiconductor device can be manufactured.
• the weight average molecular weights of the products shown in the synthesis examples of this specification are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC).
• GPC gel permeation chromatography
• the solution does not become cloudy even when cooled to room temperature, and has good solubility in propylene glycol monomethyl ether.
• GPC analysis revealed that the product in the resulting solution had a weight average molecular weight of 692 and a polydispersity of 1.31 in terms of standard polystyrene.
• the main compounds obtained in this synthesis example are represented by the following formula (1a).
• the solution does not become cloudy even when cooled to room temperature, and has good solubility in propylene glycol monomethyl ether.
• GPC analysis revealed that the product in the resulting solution had a weight average molecular weight of 901 and a degree of dispersion of 1.34 in terms of standard polystyrene.
• the main compounds obtained in this synthesis example are represented by the following formula (2a).
• the solution does not become cloudy even when cooled to room temperature, and has good solubility in propylene glycol monomethyl ether.
• GPC analysis revealed that the product in the obtained solution had a weight average molecular weight of 887 and a degree of dispersion of 1.24 in terms of standard polystyrene.
• the main compounds obtained in this synthesis example are represented by the following formula (1b).
• the solution does not become cloudy even when cooled to room temperature, and has good solubility in propylene glycol monomethyl ether.
• GPC analysis revealed that the product in the resulting solution had a weight average molecular weight of 687 and a degree of dispersion of 1.21 in terms of standard polystyrene.
• the main compounds obtained in this synthesis example are represented by the following formula (2c).
• Example 3 To 7.18 g of the solution obtained in Synthesis Example 3 (solid content: 9.9% by weight), 0.25 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries Co., Ltd.), 0.036 g of pyridinium phenolsulfonic acid, 172.63 g of propylene glycol monomethyl ether and 19.90 g of propylene glycol monomethyl ether acetate were added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 ⁇ m to obtain a composition for forming a resist underlayer film for lithography.
• Example 4 To 9.38 g of the solution obtained in Synthesis Example 4 (solid content: 9.1% by weight), 0.25 g of tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries Co., Ltd.), 0.036 g of pyridinium phenolsulfonic acid, 170.39 g of propylene glycol monomethyl ether and 19.90 g of propylene glycol monomethyl ether acetate were added and dissolved. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.05 ⁇ m to obtain a composition for forming a resist underlayer film for lithography.
• the present invention provides a resist underlayer film composition for forming a resist underlayer film capable of forming a desired resist pattern, a method for manufacturing a semiconductor substrate with a resist pattern using the resist underlayer film-forming composition, and a semiconductor device. It can be suitably used for the manufacturing method.

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