Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/20—Diluents or solvents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D165/02—Polyphenylenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G10/00—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only
  • C08G10/02—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only of aldehydes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
  • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D145/00—Coating compositions based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
  • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
  • C09D5/1662—Synthetic film-forming substance
• • 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
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
  • H10P14/6326—Deposition processes
  • H10P14/6342—Liquid deposition, e.g. spin-coating, sol-gel techniques or spray coating
• • 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
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/66—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials
  • H10P14/668—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor 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
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/68—Organic materials, e.g. photoresists
  • H10P14/683—Organic materials, e.g. photoresists carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC
• • 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
  • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
  • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
  • H10P50/286—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of organic materials
  • H10P50/287—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of organic materials by chemical means
• • 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
  • H10P50/71—Etching of wafers, substrates or parts of devices using masks for conductive or resistive 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
  • H10P50/73—Etching of wafers, substrates or parts of devices using masks for insulating 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/01—Manufacture or treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials

Definitions

• the present invention relates to a composition for forming a protective film, a protective film, a method for forming the protective film, and a method for manufacturing a patterned substrate.
• a multilayer resist process is used in which a resist film laminated on a substrate via a resist underlayer film such as an organic underlayer film or a silicon-containing film is exposed and developed to form a resist pattern. Has been done.
• the resist underlayer film is etched using this resist pattern as a mask, and the substrate is further etched using the obtained resist underlayer film pattern as a mask to form a desired pattern on the substrate to obtain a patterned substrate.
• a protective film-forming composition having excellent coatability is required for the protective film on the peripheral edge of the substrate.
• An object of the present invention is to provide a composition for forming a protective film having excellent coatability, a protective film, a method for forming the protective film, and a method for producing a patterned substrate.
• a composition for forming a protective film for forming a protective film only on the peripheral edge of the substrate A compound having an aromatic ring (hereinafter, also referred to as “[A] compound”) and Containing a solvent (hereinafter, also referred to as "[B] solvent”),
• the [A] solvent includes the [B] solvent having a standard boiling point of 156 ° C. or higher and lower than 300 ° C.
• the present invention relates to a composition for forming a protective film.
• the present invention also relates to a protective film formed from a protective film forming composition in one embodiment.
• the present invention in one embodiment, A step of directly or indirectly applying the protective film forming composition according to any one of claims 1 to 12 only to the peripheral edge of the substrate.
• the present invention relates to a method for forming a protective film.
• the present invention in one embodiment, The step of directly or indirectly applying the protective film forming composition according to any one of claims 1 to 12 only to the peripheral portion of the substrate.
• the present invention relates to a method for manufacturing a patterned substrate, which comprises a step of performing etching using the resist pattern as a mask.
• a step of directly or indirectly forming an organic underlayer film on a substrate having a protective film formed by the above coating step can be further included.
• a step of directly or indirectly forming a silicon-containing film on the substrate can be further included.
• the protective film forming composition of the present invention it is possible to form a protective film having excellent coatability at the peripheral edge of the substrate.
• the protective film of the present invention is excellent in coatability at the peripheral edge of the substrate.
• a protective film having excellent coatability can be obtained at the peripheral edge of the substrate.
• a protective film having excellent coatability can be obtained at the peripheral edge of the substrate, so that a substrate having an excellent pattern shape can be obtained. Therefore, these can be suitably used for manufacturing semiconductor devices and the like, which are expected to be further miniaturized in the future.
• composition for forming a protective film the protective film, the method for forming the protective film, and the method for producing the patterned substrate according to the embodiment of the present invention will be described in detail.
• the protective film-forming composition as a protective film-forming composition for forming a protective film only on the peripheral edge of the substrate contains the compound [A] and the solvent [B].
• the protective film-forming composition contains a second solvent (hereinafter, also referred to as “[C] solvent”), which is a solvent having a standard boiling point of less than 156 ° C., and other optional components, as long as the effects of the present invention are not impaired. It may be contained.
• the protective film forming composition is used to form a protective film only on the peripheral edge of the substrate.
• the peripheral portion of the substrate means, for example, the outer peripheral portion of the substrate whose length from the outer peripheral end portion of the substrate to the center of the substrate is within 3.0 cm.
• the lengths from the outer peripheral edge of the substrate to the center of the substrate can be 2.0 cm, 1.0 cm, and 0.5 cm.
• the substrate examples include a silicon substrate, an aluminum substrate, a nickel substrate, a chrome substrate, a molybdenum substrate, a tungsten substrate, a copper substrate, a tantalum substrate, a metal or semi-metal substrate such as a titanium substrate, and the like.
• the substrate may be a substrate on which a silicon nitride film, an alumina film, a silicon dioxide film, a tantalum nitride film, a titanium nitride film, or the like is formed.
• the compound [A] is a compound having an aromatic ring other than the solvent.
• the compound [A] can be used without particular limitation as long as it has an aromatic ring.
• the compound may be used alone or in combination of two or more.
• aromatic ring examples include, for example.
• Aromatic carbocycles such as benzene ring, naphthalene ring, anthracene ring, inden ring, pyrene ring, fluorenylidene biphenyl ring, fluorenylidene binaphthalene ring, furan ring, pyrrole ring, thiophene ring, phosphor ring, pyrazole ring, oxazole.
• aromatic heterocycles such as a ring, an isooxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, and a triazine ring.
• aromatic carbocycles are preferred.
• Examples of the compound [A] include a resin having an aromatic ring in the main chain, a resin such as a resin having no aromatic ring in the main chain and an aromatic ring in the side chain, and an aromatic ring having a molecular weight of 300 or more and 3,000 or less.
• the contained compounds and the like can be mentioned.
• the "resin” means a compound having two or more structural units.
• the "aromatic ring-containing compound” refers to a compound having one structural unit.
• the "main chain” is the longest chain composed of atoms in a resin.
• Segment chain means a chain other than the longest chain composed of atoms in a resin.
• Examples of the resin include polycondensation compounds and compounds obtained by reactions other than polycondensation.
• the resin examples include novolak resin, resol resin, styrene resin, acenaphthylene resin, triazine resin and the like.
• the novolak resin is a resin obtained by reacting a phenolic compound with an aldehyde or a divinyl compound using an acidic catalyst. A plurality of phenolic compounds may be mixed and reacted with aldehydes, divinyl compounds and the like.
• phenolic compound examples include phenol, cresol, xylenol, resorcinol, bisphenol A, p-tert-butylphenol, p-octylphenol, 9,9-bis (4-hydroxyphenyl) fluorene, and 9,9-bis (3-).
• Phenols such as hydroxyphenyl) fluorene, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 9,9-bis (6-hydroxynaphthyl) fluorene and other naphthols, 9- Examples thereof include anthrols such as anthrol and pyrenols such as 1-hydroxypyrene and 2-hydroxypyrene.
• aldehydes examples include aldehydes such as formaldehyde, benzaldehyde, 1-naphthaldehyde, 2-naphthaldehyde and 1-formylpyrene, and aldehyde sources such as paraformaldehyde and trioxane.
• divinyl compounds examples include divinylbenzene, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnoborna-2-ene, divinylpyrene, limonene, 5-vinylnorbornadiene and the like.
• novolak resin examples include dihydroxynaphthalene and a resin having a structural unit derived from formaldehyde, fluorenbisphenol and a resin having a structural unit derived from formaldehyde, fluorenbisnaphthol and a resin having a structural unit derived from formaldehyde, hydroxypyrene and the like.
• examples include resins having structural units derived from formaldehyde, resins having structural units derived from phenol compounds and formaldehyde, and resins in which some or all of the hydrogen atoms of the phenolic hydroxyl groups of these resins are replaced with propargyl groups or the like. be able to.
• the resole resin is a resin obtained by reacting a phenolic compound with aldehydes using an alkaline catalyst.
• Styrene resin is a resin having a structural unit derived from a compound having an aromatic ring and a polymerizable carbon-carbon double bond.
• the styrene resin may have structural units derived from acrylic monomers, vinyl ethers, and the like.
• styrene resin examples include polystyrene, polyvinylnaphthalene, polyhydroxystyrene, polyphenyl (meth) acrylate, and a resin combining these.
• the acenaphthylene resin is a resin having a structural unit derived from a compound having an acenaphthylene skeleton.
• acenaphthylene resin a copolymer of acenaphthylene and hydroxymethylacenaphthylene is preferable from the viewpoint of further improving the coatability of the protective film.
• the triazine resin is a resin having a structural unit derived from a compound having a triazine skeleton.
• Examples of the compound having a triazine skeleton include a melamine compound and a cyanuric acid compound.
• the polystyrene-equivalent weight average molecular weight (Mw) of the compound [A] by gel permeation chromatography (GPC) is 2,000. It is preferably more than 3,000, more preferably 3,000 or more, and even more preferably 5,000 or more.
• the Mw is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.
• calixarene resin examples include a cyclic 4- to 12-mer formed from a phenol compound such as phenol and naphthol and formaldehyde, and a cyclic 4- to 12-mer formed from a phenol compound such as phenol and naphthol and a benzaldehyde compound.
• examples thereof include resins in which the hydrogen atom of the phenolic hydroxyl group of these cyclic bodies is replaced with a propargyl group or the like.
• the aromatic ring-containing compound is a compound having an aromatic ring and having a molecular weight of 300 or more and 3,000 or less.
• the molecular weight of the aromatic ring-containing compound is, for example, a polystyrene-equivalent weight average molecular weight (Mw) by gel permeation chromatography (GPC).
• aromatic ring-containing compound examples include a compound having a fluorene bisphenol skeleton, a compound having a spiroinden skeleton, a compound having a Torxene skeleton, and a compound having a triphenylbenzene skeleton.
• the lower limit of the content ratio of the [A] polymer in the composition is preferably 2% by mass, more preferably 4% by mass, and further 5% by mass, based on the total mass of the [A] polymer and the [B] solvent. It is preferable, and 6% by mass is particularly preferable.
• the upper limit of the content ratio is preferably 30% by mass, more preferably 25% by mass, further preferably 20% by mass, and particularly preferably 18% by mass in the total mass of the polymer [A] and the solvent [B].
• [[A] Compound synthesis method] The compound [A] may be synthesized according to a known method, or a commercially available commercially available product may be used.
• the solvent of the present invention dissolves or disperses the compound [A] and any components contained as necessary.
• the solvent includes a first solvent having a standard boiling point of 156 ° C. or higher and lower than 300 ° C. (hereinafter, also referred to as “[B] solvent”). Further, the solvent may further contain a second solvent having a standard boiling point of less than 156 ° C. (hereinafter, also referred to as “[C] solvent”).
• the solvent may contain other solvents other than the [B] solvent and the [C] solvent as long as the effects of the present invention are not impaired.
• Each component of the above-mentioned [B] solvent, [C] solvent and other solvents may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.
• the content ratio of the solvent in the protective film forming composition is preferably 10% by mass or more and 90% by mass or less, and may be 20% by mass or more and 80% by mass or less.
• the solvent is a solvent having a standard boiling point of 156 ° C. or higher and lower than 300 ° C.
• the solvent contains the solvent [B], which is a high boiling point component, evaporation of the solvent during heating of the coating film is suppressed, and the fluidity of the constituent components of the coating film containing the solvent is improved. As a result, the coatability of the protective film can be improved.
• the standard boiling point of the [B] solvent is preferably 205 ° C. or higher.
• the upper limit of the standard boiling point of the solvent is preferably 250 ° C, more preferably 240 ° C, and particularly preferably 230 ° C.
• Examples of the solvent component include esters, alcohols, ethers, carbonates, ketones, amide-based solvents and the like.
• the temperature (° C.) in () of each solvent exemplified below indicates the value of the standard boiling point.
• esters examples include, for example.
• carboxylic acid esters include 2-ethylbutyl acetate (160 ° C), 2-ethylhexyl acetate (199 ° C), benzyl acetate (212 ° C), cyclohexyl acetate (172 ° C), methylcyclohexyl acetate (201 ° C), n-nonyl acetate.
• Acetic acid ester such as (208 ° C.), acetic acid ester such as methyl acetoacetate (169 ° C.), ethyl acetoacetate (181 ° C.), propionic acid ester such as iso-amyl propionate (156 ° C.), diethyl oxalate (185 ° C.). ° C.), oxalic acid ester such as di-n-butyl oxalate (239 ° C.), lactic acid ester such as n-butyl lactic acid (185 ° C.), malonic acid ester such as diethyl malonate (199 ° C.), dimethyl phthalate (°C).
• Phthalates such as 283 ° C), ⁇ -propiolactone (162 ° C), ⁇ -butyrolactone (204 ° C), ⁇ -valerolactone (207 ° C), ⁇ -undecalactone (286 ° C) and other lactones, 1 , 6-Diacetoxyhexane (260 ° C.), alkylene glycol diacetate such as 1,3-butylene glycol diacetate (232 ° C.) and the like can be mentioned.
• Examples of the alcohols include, for example.
• Examples of monoalcohols include 3-methoxybutanol (157 ° C.), n-hexanol (157 ° C.), n-octanol (194 ° C.), sec-octanol (174 ° C.), n-nonyl alcohol (215 ° C.), n-decanol. (228 ° C), phenol (182 ° C), cyclohexanol (161 ° C), benzyl alcohol (205 ° C), etc.
• polyhydric alcohols examples include ethylene glycol (197 ° C.), 1,2-propylene glycol (188 ° C.), 1,3-butylene glycol (208 ° C.), 2,4-pentanediol (201 ° C.), and 2-methyl-. 2,4-Pentanediol (196 ° C), 2,5-hexanediol (216 ° C), triethylene glycol (165 ° C), dipropylene glycol (230 ° C), glycerin (290 ° C), etc.
• ethylene glycol monobutyl ether (171 ° C), ethylene glycol monophenyl ether (244 ° C), diethylene glycol monomethyl ether (194 ° C), diethylene glycol monoethyl ether (202 ° C), triethylene glycol monomethyl ether ( 249 ° C.), Diethylene glycol monoisopropyl ether (207 ° C.), Diethylene glycol monobutyl ether (231 ° C.), Triethylene glycol monobutyl ether (271 ° C.), Ethylene glycol monoisobutyl ether (161 ° C.), Diethylene glycol monoisobutyl ether (220 ° C.), Ethylene glycol monohexyl ether (208 ° C), diethylene glycol monohexyl ether (259 ° C), ethylene glycol mono2-ethylhexyl ether (229 ° C), diethylene glycol mono2-ethylhexyl ether
• Dipropylene glycol monopropyl ether (212 ° C.), propylene glycol monobutyl ether (170 ° C.), dipropylene glycol monobutyl ether (231 ° C.), propylene glycol monophenyl ether (243 ° C.) and the like.
• Examples of the ethers include, for example.
• Examples of the dialkylene glycol monoalkyl ether acetate include dipropylene glycol monomethyl ether acetate (213 ° C.), diethylene glycol monoethyl ether acetate (217 ° C.), diethylene glycol monobutyl ether acetate (247 ° C.), and the like.
• Examples of the alkylene glycol monoalkyl ether acetates include butylene glycol monomethyl ether acetate (172 ° C.) and ethylene glycol monobutyl ether acetate (188 ° C.).
• dialkylene glycol dialkyl ethers examples include diethylene glycol dimethyl ether (162 ° C.), diethylene glycol methyl ethyl ether (176 ° C.), diethylene glycol diethyl ether (189 ° C.), diethylene glycol dibutyl ether (255 ° C.), dipropylene glycol dimethyl ether (171 ° C.), and the like.
• trialkylene glycol dialkyl ethers triethylene glycol dimethyl ether (216 ° C.) and the like are used.
• tetraalkylene glycol dialkyl ethers tetraethylene glycol dimethyl ether (275 ° C.) and the like are used.
• dihydrocarbon group ethers examples include diisopentyl ether (171 ° C.), anisole (155 ° C.), ethylbenzyl ether (189 ° C.), diphenyl ether (259 ° C.), dibenzyl ether (297 ° C.), and dihexyl ether (226 ° C.). ) Etc.
• the cyclic ethers include 1,8-cineole (176 ° C.) and the like.
• Examples of the carbonates include ethylene carbonate (244 ° C.) and propylene carbonate (242 ° C.).
• ketones examples include ethyl amylketone (167 ° C.), dibutylketone (186 ° C.), diamylketone (228 ° C.) and the like.
• amide solvent examples include N-methylpyrrolidone (204 ° C.), N, N-dimethylacetamide (165 ° C.), formamide (210 ° C.), N-ethylacetamide (206 ° C.), and N-methylacetamide (206 ° C.). °C) etc. can be raised.
• Examples of the other (A2) solvent include furfural (162 ° C.), dimethyl sulfoxide (189 ° C.), sulfolane (287 ° C.), succinonitrile (265 ° C.), nitrobenzene (211 ° C.), and the like.
• esters, alcohols, ethers, carbonates or combinations thereof are preferable, and carboxylic acid esters, monoalcohols, polyhydric alcohols, polyhydric alcohol partial ethers, dialkylene glycol monoalkyl ethers.
• Acetates and dialkylene glycol dialkyl ethers are more preferable, ⁇ -butyrolactone, benzyl alcohol, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and propylene carbonate are more preferable, and dipropylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate are particularly preferable.
• the upper limit of the value of the relative evaporation rate of the [B] solvent 10 is preferable, 8 is more preferable, 6 is more preferable, and 4 is particularly preferable when the evaporation rate of butyl acetate is 100.
• the "relative evaporation rate” means the value of the evaporation rate measured according to ASTM-D3539 under the condition of 25 ° C. and 1 atm.
• the numerical value in () of each solvent indicates the value of the relative evaporation rate when butyl acetate is 100), for example, propylene glycol.
• the viscosity of the solvent is preferably 0.8 mPa ⁇ s or more and 10.0 mPa ⁇ s or less.
• viscosity indicates the difficulty of flowing a liquid (fluid) of a substance, and is also referred to as viscosity.
• viscosity the value measured at 25 ° C. described in "Solvent Handbook” or the like can be referred to.
• the viscosity of the solvent not described in the above solvent handbook is a value measured at 25 ° C. by the method described in JIS-Z8803: 2011.
• the lower limit of the viscosity of the solvent is preferably 1.0 mPa ⁇ s, more preferably 1.5 mPa ⁇ s.
• the upper limit of the viscosity of the solvent [B] is preferably 8.0 mPa ⁇ s, more preferably 6.0 mPa ⁇ s, further preferably 5.0 mPa ⁇ s, and particularly preferably 3.5 mPa ⁇ s.
• the numerical value in () of each solvent indicates the value of the viscosity at 25 ° C.
• dipropylene glycol monomethyl ether acetate 1.7 mPa ⁇ s.
• Diethylene glycol monoethyl ether acetate 2.5 mPa ⁇ s
• Diethylene glycol monobutyl ether acetate 3.1 mPa ⁇ s
• Dipropylene glycol dimethyl ether 1.0 mPa ⁇ s
• Dipropylene glycol monomethyl ether (3.6 mPa ⁇ s).
• Dipropylene glycol monobutyl ether (4.5 mPa ⁇ s), tripropylene glycol monomethyl ether (5.3 mPa ⁇ s), ⁇ -butyrolactone (1.8 mPa ⁇ s), propylene carbonate (2.3 mPa ⁇ s), tetra.
• Ethylene glycol dimethyl ether (3.8 mPa ⁇ s), 1,6-diacetoxyhexane (3.9 mPa ⁇ s), dipropylene glycol (20 mPa ⁇ s), 1,3-butylene glycol diacetate (2.9 mPa ⁇ s) Etc. can be given.
• the content ratio of the [B] solvent in the solvent in the protective film forming composition can be, for example, 0.1% by mass or more and less than 100% by mass.
• the lower limit of the content ratio 10% by mass is more preferable, 30% by mass is further preferable, 40% by mass is particularly preferable, and 45% by mass is further particularly preferable.
• the coatability can be further improved.
• the upper limit of the content ratio 80% by mass is more preferable, 70% by mass is further preferable, 60% by mass is particularly preferable, and 55% by mass is further particularly preferable.
• the coatability can be further improved.
• the solvent is a solvent having a standard boiling point of less than 156 ° C.
• the upper limit of the standard boiling point of the solvent is preferably 155 ° C, more preferably 147 ° C.
• the lower limit of the standard boiling point of the solvent is preferably 100 ° C, more preferably 120 ° C.
• monoalcohols include methanol (65 ° C), ethanol (78 ° C), n-propanol (97 ° C), iso-propanol (82 ° C), n-butanol (117 ° C), iso-butanol (108 ° C), sec.
• carboxylic acid esters examples include propionic acid esters such as iso-butyl propionic acid (138 ° C.) and lactic acid esters such as ethyl lactate (151 ° C.).
• alkylene glycol monoalkyl ethers examples include ethylene glycol monomethyl ether (125 ° C), ethylene glycol monoethyl ether (135 ° C), propylene glycol monomethyl ether (121 ° C), propylene glycol monoethyl ether (133 ° C), and propylene glycol monopropyl. Ether (149.8 ° C) etc.
• alkylene glycol monoalkyl ether acetates include ethylene glycol monomethyl ether acetate (145 ° C.) and propylene glycol monomethyl ether acetate (146 ° C.).
• the solvent [C] is preferably alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, or a combination thereof, preferably propylene.
• Glycol monoalkyl ether acetates are more preferred, and propylene glycol monomethyl ether acetates are even more preferred.
• the lower limit of the content ratio of the [C] solvent in the solvent in the protective film forming composition 10% by mass is more preferable, 30% by mass is further preferable, 40% by mass is particularly preferable, and 45% by mass is further particularly preferable. .. Further, as the upper limit of the content ratio, 80% by mass is more preferable, 70% by mass is further preferable, 60% by mass is particularly preferable, and 55% by mass is further particularly preferable. [C] By setting the content ratio of the solvent in the above range, the coatability can be further improved.
• the protective film-forming composition contains, for example, an acid generator, a polymer additive, a surfactant, a cross-linking agent, and the like as components other than the [A] compound, the [B] solvent, and the [C] solvent. be able to.
• the acid generator is a compound that generates acid by irradiation and / or heating with radiation.
• the protective film-forming composition may contain one or more acid generators.
• Examples of the acid generator include onium salt compounds and N-sulfonyloxyimide compounds.
• polymer additive examples include (poly) oxyalkylene polymer compounds, fluorine-containing polymer compounds, non-fluoropolymer compounds and the like.
• Examples of the (poly) oxyalkylene polymer compound include polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adduct, diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, and polyoxyethylene.
• polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adduct, diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, and polyoxyethylene.
• Polyoxypropylene-2-ethylhexyl ethers such as oxyethyleneoxypropylene adducts to higher alcohols having 12 to 14 carbon atoms, polyoxypropylene phenyl ethers, polyoxyethylene nonylphenyl ethers and the like
• Poly Oxyalkylene (alkyl) aryl ethers, 2,4,7,9-tetramethyl-5-decine-4,7-diol, 2,5-dimethyl-3-hexine-2,5-diol, 3-
• Oxyalkylene fatty acid esters such as acetylene ethers obtained by addition-polymerizing alkylene oxide to acetylene alcohol such as methyl-1-butin-3-ol, diethylene glycol oleic acid ester, diethylene glycol lauric acid ester, and ethylene glycol distearate ester.
• Polyoxyethylene sorbitan monolauric acid ester (poly) oxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleic acid ester, polyoxypropylene methyl ether sodium sulfate, polyoxyethylene dodecylphenol ether sodium sulfate (poly) Oxyalkylene alkyl (aryl) ether sulfate ester salts, (poly) oxyalkylene alkyl phosphates such as (poly) oxyethylene stearyl phosphate, (poly) oxyalkylene alkyl amines such as polyoxyethylene laurylamine, etc. Can be mentioned.
• fluorine-containing polymer compound examples include a repeating unit derived from a (meth) acrylate compound having a fluorine atom and two or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups). Examples thereof include compounds containing a repeating unit derived from a (meth) acrylate compound having.
• non-fluoropolymer compound examples include lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, and isostearyl (meth).
• Examples thereof include compounds containing one or more repeating units
• surfactants include, for example, “Newcol 2320”, “Newcol 714-F”, “Newcol 723”, “Newcol 2307”, “Newcol 2303” (all manufactured by Nippon Emulsorium Co., Ltd.), and “Pionin”.
• the cross-linking agent is a component that forms a cross-linking bond between components such as the [A] compound by the action of heat or acid. Even when the compound [A] has an intermolecular bond-forming group, the protective film-forming composition can further increase the hardness of the protective film by further containing a cross-linking agent.
• the cross-linking agent may be used alone or in combination of two or more.
• cross-linking agent examples include polyfunctional (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate, epoxy compounds such as novolak type epoxy resin and bisphenol type epoxy resin, and 2-hydroxy.
• polyfunctional (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate
• epoxy compounds such as novolak type epoxy resin and bisphenol type epoxy resin, and 2-hydroxy.
• Methyl-4,6-dimethylphenol 4,4'-(1- (4- (1- (4-hydroxy-3,5-bis (methoxymethyl) phenyl) -1-methylethyl) phenyl) ethylidene) bis Hydroxymethyl group-substituted phenol compounds such as (2,6-bis (methoxymethyl) phenol), methoxymethyl group-containing phenol compounds, alkoxyalkyl group-containing phenol compounds such as ethoxymethyl group-containing phenol compounds, (poly) methylolated melamine, Examples thereof include compounds having an alkoxyalkylated amino group such as (poly) methylolated glycol uryl.
• the lower limit of the content of the other optional components is preferably 0.1 part by mass, preferably 0.5 part by mass with respect to 100 parts by mass of the compound [A]. Parts by mass are more preferred, and parts by mass are even more preferred.
• the upper limit of the content is preferably 20 parts by mass, more preferably 10 parts by mass, and even more preferably 5 parts by mass.
• the protective film-forming composition is preferably a mixture obtained by mixing [A] compound, [B] solvent, and if necessary, [C] solvent, [D] and other optional components in a predetermined ratio.
• the protective film of the present invention is formed from the protective film forming composition.
• the protective film has excellent coatability.
• the method for forming the protective film of the present invention is A step of directly or indirectly applying the protective film forming composition only to the peripheral portion of the substrate (hereinafter, also referred to as “coating step”) is included.
• the composition for forming the protective film is used in the coating process, it is possible to form a protective film having excellent coatability.
• the method for forming the protective film further includes a step of heating the coating film formed by the above coating step (hereinafter, also referred to as "heating step").
• the protective film forming composition is directly or indirectly applied only to the peripheral edge of the substrate.
• the above coating method can be carried out by rotary coating.
• a coating film is formed by rotating the substrate and discharging the protective film-forming composition on the peripheral edge of the substrate, and the cross-linking reaction of the compound [A] contained in the coating film and the volatilization of the solvent are carried out. By happening, a protective film is formed.
• the heating of the coating film is usually performed in the atmosphere, but may be performed in a nitrogen atmosphere.
• As the lower limit of the temperature in heating 150 ° C. is preferable, and 200 ° C. is more preferable.
• the upper limit of the temperature is preferably 600 ° C, more preferably 400 ° C.
• the lower limit of the heating time is preferably 15 seconds, more preferably 30 seconds.
• the upper limit of the time is preferably 1,200 seconds, more preferably 600 seconds.
• the lower limit of the average thickness of the protective film formed is preferably 30 nm, more preferably 50 nm, and even more preferably 100 nm.
• the upper limit of the average thickness is preferably 3,000 nm, more preferably 2,000 nm, and even more preferably 500 nm.
• the average thickness of the protective film is such that the protective film-forming composition is discharged to the center of the substrate, and the film formed by the protective film-forming composition over the entire substrate by the rotary coating method is measured by a spectroscopic ellipsometer (JA. It is a value obtained by measuring the film thickness at arbitrary 9 points at intervals of 5 cm including the center of the substrate using "M2000D" manufactured by WOOLLAM, and calculating the average value of those film thicknesses.
• the method for manufacturing the patterned substrate is as follows.
• a step of directly or indirectly applying the protective film forming composition only to the peripheral portion of the substrate (hereinafter, also referred to as “coating step”).
• a step of directly or indirectly forming a resist pattern on a substrate having the protective film formed by the above coating step (hereinafter, also referred to as “resist pattern forming step”). It includes a step of performing etching using the resist pattern as a mask (hereinafter, also referred to as an “etching step”).
• the protective film having excellent coatability is formed in the coating process, so that the patterned substrate having a good pattern shape can be manufactured.
• the method for manufacturing the patterned substrate directly or indirectly forms an organic underlayer film on the substrate having the protective film formed by the coating process before the resist pattern forming step, if necessary.
• a step (hereinafter, also referred to as an “organic underlayer film forming step”) may be further provided.
• the method for manufacturing the patterned substrate directly or indirectly forms a silicon-containing film on the substrate having the protective film formed by the coating process before the resist pattern forming step, if necessary.
• a step (hereinafter, also referred to as a “silicon-containing film forming step”) may be further provided.
• the protective film forming composition is directly or indirectly applied only to the peripheral portion of the substrate. This step is the same as the coating step in the method for forming the protective film described above.
• Organic underlayer film forming process In this step, an organic underlayer film is directly or indirectly formed on the substrate having the protective film.
• the organic underlayer film can be formed by coating an organic underlayer film forming composition or the like.
• a method of forming the organic underlayer film by coating the composition for forming the organic underlayer film for example, the coating formed by directly or indirectly applying the composition for forming the organic underlayer film to the substrate having the protective film. Examples thereof include a method of curing the film by heating or exposing the film.
• the composition for forming an organic underlayer film for example, "HM8006" manufactured by JSR Corporation can be used. Various conditions of heating and exposure can be appropriately determined depending on the type of the organic underlayer film forming composition to be used and the like.
• Silicon-containing film forming step In this step, a silicon-containing film is directly or indirectly formed on the substrate having the protective film.
• the silicon-containing film can be formed by coating a composition for forming a silicon-containing film, a chemical vapor deposition (CVD) method, an atomic layer deposition (ALD), or the like.
• a method of forming a silicon-containing film by coating a silicon-containing film-forming composition for example, a coating formed by directly or indirectly applying a silicon-containing film-forming composition to the protective film. Examples thereof include a method of curing the film by exposing and / or heating it.
• a commercially available product for forming the silicon-containing film for example, "NFC SOG01", “NFC SOG04", “NFC SOG080" (all manufactured by JSR Corporation) and the like can be used.
• a silicon oxide film, a silicon nitride film, a silicon nitride film, or an amorphous silicon film can be formed by a chemical vapor deposition (CVD) method or an atomic layer deposition (ALD).
• a resist pattern is formed directly or indirectly on the protective film.
• the method for performing this step include a method using a resist composition, a method using a nanoimprint method, and a method using a self-assembling composition.
• cases where a resist pattern is indirectly formed on the protective film include a case where the method for manufacturing the patterned substrate includes the silicon-containing film forming step and a case where the resist pattern is formed on the silicon-containing film. Can be given.
• the method using the resist composition is to volatilize the solvent in the coating film by applying the resist composition so that the resist film to be formed has a predetermined thickness and then prebaking the resist composition. To form a resist film.
• the resist composition examples include a positive-type or negative-type chemically amplified resist composition containing a radiation-sensitive acid generator, a positive-type resist composition containing an alkali-soluble resin and a quinonediazide-based photosensitive agent, and an alkali.
• examples thereof include a negative resist composition containing a soluble resin and a cross-linking agent.
• a commercially available resist composition can be used as it is.
• the radiation used for the exposure can be appropriately selected depending on the type of the radiation-sensitive acid generator used in the resist composition, and for example, visible light, ultraviolet rays, far ultraviolet rays, X-rays, ⁇ -rays and the like can be selected. Examples include electromagnetic waves, electron beams, molecular beams, particle beams such as ion beams, and the like. Among these, far ultraviolet rays are preferable, and KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F2 excimer laser light (wavelength 157 nm), Kr2 excimer laser light ( wavelength 147 nm), ArKr excimer laser light.
• post-baking can be performed to improve the resolution, pattern profile, developability, etc.
• the temperature and time of this post-bake can be appropriately determined depending on the type of resist composition used and the like.
• the exposed resist film is developed with a developing solution to form a resist pattern.
• This development may be alkaline development or organic solvent development.
• the developing solution include basic aqueous solutions such as ammonia, triethanolamine, tetramethylammonium hydroxide (TMAH), and tetraethylammonium hydroxide in the case of alkaline development.
• An appropriate amount of a water-soluble organic solvent such as alcohols such as methanol and ethanol, a surfactant and the like can be added to these basic aqueous solutions.
• examples of the developing solution include various organic solvents exemplified as the [B] solvent of the above-mentioned composition.
• a predetermined resist pattern is formed by washing and drying after development with the above developer.
• etching is performed using the resist pattern as a mask.
• the number of times of etching may be once or a plurality of times, that is, the pattern obtained by etching may be used as a mask for sequential etching, but from the viewpoint of obtaining a pattern having a better shape, a plurality of times is preferable.
• the silicon-containing film, the protective film, and the substrate are etched in this order.
• the etching method include dry etching and wet etching. Among these, dry etching is preferable from the viewpoint of improving the shape of the pattern on the substrate.
• gas plasma such as oxygen plasma is used.
• the dry etching can be performed using, for example, a known dry etching apparatus.
• the etching gas used for dry etching can be appropriately selected depending on the mask pattern, the elemental composition of the film to be etched, and the like. For example, CHF 3 , CF 4 , C 2 F 6 , C 3 F 8 , SF 6 , etc.
• Fluorine gas chlorine gas such as Cl 2 , BCl 3 , oxygen gas such as O 2 , O 3 , H 2 O, H 2 , NH 3 , CO, CO 2 , CH 4 , C 2 H 2 , Reducing gases such as C 2 H 4 , C 2 H 6 , C 3 H 4 , C 3 H 6 , C 3 H 8 , HF, HI, HBr, HCl, NO, NH 3 , BCl 3 , etc., He, N 2 , Ar and other inert gases can be mentioned. These gases can also be mixed and used. When the substrate is etched using the protective film pattern as a mask, a fluorine-based gas is usually used.
• Mw Weight average molecular weight
• the Mw of the polymer used was a GPC column manufactured by Toso Co., Ltd. (2 “G2000HXL”, 1 “G3000HXL”, and 1 “G4000HXL”), flow rate: 1.0 mL / min, elution solvent: tetrahydrofuran. , Column temperature: 40 ° C., measured by gel permeation chromatography (detector: differential refraction meter) using monodisperse polystyrene as a standard.
• the average thickness of the protective film is such that the protective film-forming composition is ejected to the center of the substrate, and the film formed by the protective film-forming composition is spread over the entire substrate by the rotary coating method. This is a value obtained by measuring the film thickness at arbitrary 9 points at intervals of 5 cm including the center of the substrate using "M2000D" manufactured by M2000D) and calculating the average value of those film thicknesses.
• A-1 Resin having a structural unit represented by the following formula (A-1)
• A-2 Resin having a structural unit represented by the following formula (A-2)
• A-3 Resin having a structural unit represented by the following formula (A-2)
• A-4 A resin having a structural unit represented by the following formula (A-4).
• the number attached to the structural unit of the above formula (A-1) indicates the content ratio (mol%) of the structural unit.
• * R indicates a site bonded to an oxygen atom.
• the reaction solution was put into a mixed solution of methanol / water (50/50 (mass ratio)) and reprecipitated.
• the precipitate was collected with a filter paper and dried to obtain a polymer (A-1).
• the Mw of the polymer (A-1) was 50,000.
• B-1 1,6-diacetoxyhexane (standard boiling point: 260 ° C)
• B-2 Carbonic acid carbonate (standard boiling point: 242 ° C)
• B-3 Dipropylene glyco-lmethylether acetate (standard boiling point: 213 ° C)
• B-4 Gamma-Butyrolactone (standard boiling point: 204 ° C)
• B-5 Tripropylene glycol monomethyl ether (standard boiling point: 242 ° C)
• B-6 Ethyl 3-ethoxypropionate (standard boiling point: 170 ° C)
• D-1 Surfactant ("NBX-15” manufactured by Neos Co., Ltd.)
• D-2 Surfactant ("F563" manufactured by DIC Corporation)
• D-3 Poly (2-ethylhexyl acrylate)
• Example 1 (Preparation of protective film forming composition (J-1)) [A] 10 parts by mass of (A-1) as a compound was dissolved in 100 parts by mass of (B-1) as a solvent of [B]. This solution was filtered through a polytetrafluoroethylene (PTFE) filter having a pore size of 0.2 ⁇ m to prepare a protective film-forming composition (J-1).
• PTFE polytetrafluoroethylene
• the protective film forming composition of the present invention it is possible to form a protective film having excellent coatability at the peripheral edge of the substrate.
• the protective film of the present invention is excellent in coatability at the peripheral edge of the substrate.
• a protective film having excellent coatability can be obtained at the peripheral edge of the substrate.
• a protective film having excellent coatability can be obtained at the peripheral edge of the substrate, so that a substrate having an excellent pattern shape can be obtained. Therefore, these can be suitably used for manufacturing semiconductor devices and the like, which are expected to be further miniaturized in the future.

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• 2021
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