Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/43—Solvents
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/26—Organic compounds containing oxygen
  • C11D7/265—Carboxylic acids or salts thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/50—Solvents
  • C11D7/5004—Organic solvents
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/50—Solvents
  • C11D7/5004—Organic solvents
  • C11D7/5009—Organic solvents containing phosphorus, sulfur or silicon, e.g. dimethylsulfoxide
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/50—Solvents
  • C11D7/5004—Organic solvents
  • C11D7/5022—Organic solvents containing oxygen
• • 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
  • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
  • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/16—Coating processes; Apparatus therefor
• • 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
  • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
• • 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
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces
  • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

Definitions

• the present invention relates to a method for manufacturing a semiconductor substrate, a method for forming a resist underlayer film, and a cleaning liquid.
• a metal hard mask composition which is a resist underlayer film, has been proposed in the manufacture of semiconductor substrates and the like (see Japanese Patent Laid-Open No. 2013-185155).
• Clean Track manufactured by Tokyo Electron Co., Ltd.
• This apparatus is an apparatus that can consistently perform processes such as spin coating, EBR (Edge Bead Removal), back rinse, and baking.
• EBR is a process in which, after forming a film on a substrate (wafer) by spin coating, it is washed with a cleaning liquid for the purpose of removing the film from the edge portion (peripheral portion) of the substrate.
• EBR edge portion of the substrate can be cleaned by EBR.
• a cleaning solution used in EBR a mixed solution of propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether (30:70, mass ratio) is widely used in the EBR process of resist films, silicon-containing films, and organic underlayer films. used.
• the cleaning liquid is required to have cleaning properties such as removal of the metal hard mask at the peripheral edge of the substrate.
• cleaning properties such as removal of the metal hard mask at the peripheral edge of the substrate.
• waste liquids from multiple processes are often discharged through the same pipe. Drainage stability is required to suppress unintended events such as metal deposition.
• the present invention has been made in view of the circumstances described above, and aims to provide a method for manufacturing a semiconductor substrate using a cleaning liquid that is excellent in the cleaning performance of the periphery of the substrate and in the stability of the drained liquid, and the formation of a resist underlayer film.
• the object is to provide a method and a cleaning solution.
• the present invention in one embodiment, a step of directly or indirectly coating a substrate with a composition for forming a resist underlayer film; cleaning the periphery of the substrate with a cleaning liquid; After the cleaning step, a step of directly or indirectly forming a resist pattern on the resist underlayer film formed by the coating step; including
• the composition for forming a resist underlayer film is a metal compound (hereinafter also referred to as "[A] compound”); containing a solvent (hereinafter also referred to as "[B] solvent”) and
• the present invention relates to a method for manufacturing a semiconductor substrate, wherein the cleaning liquid contains an organic acid (hereinafter also referred to as "[E] organic acid").
• the composition for forming a resist underlayer film is a metal compound; containing a solvent and
• the present invention relates to a method for forming a resist underlayer film, wherein the cleaning liquid contains an organic acid.
• a step of directly or indirectly applying a composition for forming a resist underlayer film onto a substrate A cleaning solution used in a method for manufacturing a semiconductor substrate, comprising a step of cleaning the periphery of the substrate with a cleaning solution,
• the composition for forming a resist underlayer film is a metal compound; containing a solvent and
• the cleaning liquid described above contains an organic acid.
• the periphery of the substrate is cleaned using a cleaning liquid that is excellent in cleaning performance and drainage stability, so it is possible to efficiently manufacture high-quality semiconductor substrates.
• a desired resist underlayer film can be efficiently formed because a cleaning liquid that is excellent in cleaning properties and drainage stability is used.
• the cleaning liquid is excellent in both detergency and drainage stability. Therefore, these can be suitably used for the manufacture of semiconductor devices, etc., which are expected to be further miniaturized in the future.
• a method for manufacturing a semiconductor substrate, a method for forming a resist underlayer film, and a cleaning solution according to each embodiment of the present invention will be described below. Combinations of preferred embodiments are also preferred.
• the method for manufacturing a semiconductor substrate includes a step of directly or indirectly coating a substrate with a composition for forming a resist underlayer film (hereinafter also referred to as the "composition”) (hereinafter also referred to as the “coating step”). and a step of cleaning the periphery of the substrate with a cleaning solution (hereinafter also referred to as a “cleaning step”), and after the cleaning step, directly or indirectly applying a resist pattern to the resist underlayer film formed by the coating step (hereinafter also referred to as “resist pattern forming step”).
• the method for manufacturing a semiconductor substrate preferably includes a step of forming a pattern in the resist underlayer film by etching using the resist pattern as a mask (hereinafter also referred to as an "etching step").
• the peripheral portion of the substrate refers to, for example, the peripheral portion of the substrate whose length from the peripheral edge of the substrate to the center of the substrate is within 3.0 cm.
• the length from the outer peripheral edge of the substrate to the center of the substrate can be 2.0 cm, 1.0 cm, 0.5 cm, and 0.2 cm.
• an organic underlayer film is formed directly or indirectly on the substrate having the resist underlayer film formed by the coating step.
• a step (hereinafter also referred to as an “organic underlayer film forming step”) may be further included.
• a silicon-containing film is formed, if necessary, directly or indirectly on the substrate having the resist underlayer film formed by the coating step, before the resist pattern forming step.
• a step (hereinafter also referred to as a “silicon-containing film forming step”) may be further included.
• composition for forming a resist underlayer film and the cleaning solution used in the method for manufacturing the semiconductor substrate and the optional steps of forming an organic underlayer film and forming a silicon-containing film will be described.
• composition for forming resist underlayer film contains [A] compound and [B] solvent.
• the composition may contain other optional components as long as the effects of the present invention are not impaired.
• a compound refers to a compound containing a metal atom and an oxygen atom.
• metal atoms constituting the compound include metal atoms of Groups 3 to 16 of the periodic table (excluding silicon atoms).
• the compound may have one or more metal atoms.
• Group 3 metal atoms include, for example, scandium, yttrium, lanthanum, cerium, etc.
• Examples of Group 4 metal atoms include titanium, zirconium, hafnium, etc.
• Examples of Group 5 metal atoms include vanadium, niobium, tantalum, etc.
• Examples of Group 6 metal atoms include chromium, molybdenum, tungsten, etc.
• Group 7 metal atoms include manganese, rhenium, etc.
• Group 8 metal atoms include iron, ruthenium, osmium, etc.
• Group 9 metal atoms include cobalt, rhodium, iridium, etc.
• Examples of Group 10 metal atoms include nickel, palladium, platinum, etc.
• Examples of group 11 metal atoms include copper, silver, gold, etc.
• Group 12 metal atoms include zinc, cadmium, mercury, etc.
• Examples of group 13 metal atoms include aluminum, gallium, indium, etc.
• Group 14 metal atoms include germanium, tin, lead, etc.
• Examples of group 15 metal atoms include antimony, bismuth, etc.
• Examples of Group 16 metal atoms include tellurium and the like.
• the metal atoms constituting the above [A] compound are preferably metal atoms of groups 3 to 16, more preferably metal atoms of groups 4 to 14, groups 4, 5 and 14. Group metal atoms are more preferred, and Group 4 metal atoms are particularly preferred. Specifically, titanium, zirconium, hafnium, tantalum, tungsten, tin, or combinations thereof are more preferred.
• Components other than metal atoms constituting the above [A] compound include organic acids (hereinafter also referred to as “[a] organic acids”), hydroxy acid esters, ⁇ - Diketones, ⁇ , ⁇ -dicarboxylic acid esters and amine compounds are preferred.
• organic acid refers to an organic compound exhibiting acidity
• organic compound refers to a compound having at least one carbon atom.
• organic acids include carboxylic acids, sulfonic acids, sulfinic acids, organic phosphinic acids, organic phosphonic acids, phenols, enols, thiols, acid imides, oximes, and sulfonamides.
• carboxylic acid examples include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, 2-ethylhexanoic acid, oleic acid, acrylic acid, and methacrylic acid.
• trans-2,3-dimethylacrylic acid stearic acid, linoleic acid, linolenic acid, arachidonic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, pentafluoropropion Monocarboxylic acids such as acid, gallic acid, shikimic acid, and dicarboxylic acids such as oxalic acid, malonic acid, maleic acid, methylmalonic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, and tartaric acid. and carboxylic acids having 3 or more carboxyl groups such as citric acid.
• sulfonic acid examples include benzenesulfonic acid and p-toluenesulfonic acid.
• sulfinic acid examples include benzenesulfinic acid and p-toluenesulfinic acid.
• organic phosphinic acid examples include diethylphosphinic acid, methylphenylphosphinic acid, and diphenylphosphinic acid.
• organic phosphonic acid examples include methylphosphonic acid, ethylphosphonic acid, t-butylphosphonic acid, cyclohexylphosphonic acid, and phenylphosphonic acid.
• phenols examples include monohydric phenols such as phenol, cresol, 2,6-xylenol, and naphthol; Dihydric phenols such as catechol, resorcinol, hydroquinone, 1,2-naphthalenediol; Trivalent or higher phenols such as pyrogallol and 2,3,6-naphthalenetriol can be mentioned.
• monohydric phenols such as phenol, cresol, 2,6-xylenol, and naphthol
• Dihydric phenols such as catechol, resorcinol, hydroquinone, 1,2-naphthalenediol
• Trivalent or higher phenols such as pyrogallol and 2,3,6-naphthalenetriol can be mentioned.
• Examples of the enol include 2-hydroxy-3-methyl-2-butene, 3-hydroxy-4-methyl-3-hexene, and the like.
• thiols examples include mercaptoethanol and mercaptopropanol.
• the acid imide examples include carboxylic acid imides such as maleimide and succinimide, and sulfonic acid imides such as di(trifluoromethanesulfonic acid)imide and di(pentafluoroethanesulfonic acid)imide. be able to.
• oxime examples include aldoxime such as benzaldoxime and salicylaldoxime, and ketoxime such as diethylketoxime, methylethylketoxime and cyclohexanone oxime.
• aldoxime such as benzaldoxime and salicylaldoxime
• ketoxime such as diethylketoxime, methylethylketoxime and cyclohexanone oxime.
• sulfonamide examples include methylsulfonamide, ethylsulfonamide, benzenesulfonamide, and toluenesulfonamide.
• carboxylic acid is preferable, monocarboxylic acid is more preferable, and methacrylic acid and benzoic acid are more preferable.
• hydroxy acid ester examples include glycolic acid ester, lactic acid ester, 2-hydroxycyclohexane-1-carboxylic acid ester, salicylic acid ester, and the like.
• Examples of the ⁇ -diketone include 2,4-pentanedione, 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, and the like.
• ⁇ -ketoester examples include acetoacetate, ⁇ -alkyl-substituted acetoacetate, ⁇ -ketopentanoate, benzoylacetate, and 1,3-acetonedicarboxylate.
• ⁇ -ketoester examples include acetoacetate, ⁇ -alkyl-substituted acetoacetate, ⁇ -ketopentanoate, benzoylacetate, and 1,3-acetonedicarboxylate.
• Examples of amine compounds include diethanolamine and triethanolamine.
• the compound [A] is preferably a metal compound composed of a metal atom and [a] an organic acid, and a metal compound composed of a metal atom of Groups 4, 5 and 14 and a carboxylic acid is More preferred are metal compounds composed of titanium, zirconium, hafnium, tantalum, tungsten or tin and methacrylic acid or benzoic acid.
• the form in which the [a] organic acid is contained in the [A] compound also includes an organic acid anion obtained by removing the hydrogen ion from the [a] organic acid.
• the [A] compound may contain one or more of the above metal compounds.
• the [A] compound may contain one or more [a] organic acids.
• the lower limit of the content of the [A] compound in all components contained in the composition is preferably 2% by mass, more preferably 4% by mass, and even more preferably 6% by mass.
• the upper limit of the content ratio is preferably 30% by mass, more preferably 20% by mass, and even more preferably 15% by mass.
• the [A] compound is, for example, a method of performing a hydrolytic condensation reaction using a metal-containing compound (hereinafter also referred to as "[b] metal-containing compound"), [b] ligand exchange using a metal-containing compound It can be synthesized by a method of performing a reaction or the like.
• the "hydrolytic condensation reaction” means that [b] the hydrolyzable group of the metal-containing compound is hydrolyzed and converted to -OH, and the resulting two -OH are dehydrated and condensed to -O- refers to the reaction in which is formed.
• the metal-containing compound includes a metal compound (b1) having a hydrolyzable group, a hydrolyzate of the metal compound (b1) having a hydrolyzable group, and a hydrolyzate of the metal compound (b1) having a hydrolyzable group. condensates or combinations thereof.
• the metal compound (b1) can be used singly or in combination of two or more.
• hydrolyzable group examples include halogen atoms, alkoxy groups, acyloxy groups, and the like.
• halogen atom examples include fluorine atom, chlorine atom, bromine atom, and iodine atom.
• alkoxy group examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group and the like.
• acyloxy group examples include an acetoxy group, an ethylyloxy group, a propionyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group, an n-hexanecarbonyloxy group, and an n-octanecarbonyloxy group.
• an alkoxy group and an acyloxy group are preferable, and an isopropoxy group and an acetoxy group are more preferable.
• the hydrolytic condensate of the metal compound (b1) contains a hydrolyzable group as long as the effects of the present invention are not impaired. It may be a hydrolytic condensate of a metal compound (b1) having a metalloid atom and a compound containing a metalloid atom. That is, the hydrolytic condensate of the metal compound (b1) may contain metalloid atoms within a range that does not impair the effects of the present invention. Examples of the metalloid atoms include silicon, boron, germanium, antimony, and tellurium.
• the content of metalloid atoms in the hydrolytic condensate of the metal compound (b1) is usually less than 50 atomic % with respect to the total of metal atoms and metalloid atoms in the hydrolytic condensate.
• the upper limit of the metalloid atom content is preferably 30 atomic %, more preferably 10 atomic %, relative to the sum of the metal atoms and metalloid atoms in the hydrolyzed condensate.
• Examples of the metal compound (b1) include compounds represented by the following formula ( ⁇ ) (hereinafter also referred to as "[m] compounds").
• M is a metal atom.
• L is a ligand.
• a is an integer from 0 to 2; When a is 2, multiple Ls may be the same or different.
• Y is a hydrolyzable group selected from halogen atoms, alkoxy groups and acyloxy groups.
• b is an integer from 2 to 6; Multiple Y's may be the same or different. Note that L is a ligand that does not correspond to Y.
• Examples of the metal atom represented by M include the same metal atoms as those exemplified as the metal atoms constituting the metal compound contained in the [A] compound.
• ligand represented by L monodentate ligands and polydentate ligands can be mentioned.
• Examples of the monodentate ligand include hydroxo ligands, carboxyl ligands, amide ligands, and ammonia.
• amide ligand examples include unsubstituted amide ligand (NH 2 ), methylamide ligand (NHMe), dimethylamide ligand (NMe 2 ), diethylamide ligand (NEt 2 ), dipropyl An amide ligand (NPr 2 ) and the like can be mentioned.
• polydentate ligand examples include hydroxy acid esters, ⁇ -diketones, ⁇ -ketoesters, ⁇ -dicarboxylic acid esters, hydrocarbons having ⁇ bonds, and diphosphines.
• hydroxy acid ester examples include glycolic acid ester, lactic acid ester, 2-hydroxycyclohexane-1-carboxylic acid ester, salicylic acid ester, and the like.
• Examples of the ⁇ -diketone include 2,4-pentanedione, 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, and the like.
• ⁇ -ketoester examples include acetoacetate, ⁇ -alkyl-substituted acetoacetate, ⁇ -ketopentanoate, benzoylacetate, and 1,3-acetonedicarboxylate.
• ⁇ -dicarboxylic acid esters examples include malonic acid diesters, ⁇ -alkyl-substituted malonic acid diesters, ⁇ -cycloalkyl-substituted malonic acid diesters, and ⁇ -aryl-substituted malonic acid diesters.
• hydrocarbons having a ⁇ bond examples include: Chain olefins such as ethylene and propylene; Cyclic olefins such as cyclopentene, cyclohexene, norbornene; Chain dienes such as butadiene and isoprene; Cyclic dienes such as cyclopentadiene, methylcyclopentadiene, pentamethylcyclopentadiene, cyclohexadiene and norbornadiene; Aromatic hydrocarbons such as benzene, toluene, xylene, hexamethylbenzene, naphthalene and indene can be used.
• Chain olefins such as ethylene and propylene
• Cyclic olefins such as cyclopentene, cyclohexene, norbornene
• Chain dienes such as butadiene and isoprene
• Cyclic dienes such as cyclopentadiene, methyl
• diphosphines examples include 1,1-bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 2,2′-bis( diphenylphosphino)-1,1'-binaphthyl, 1,1'-bis(diphenylphosphino)ferrocene and the like.
• halogen atom represented by Y for example, fluorine atom, chlorine atom, bromine atom, iodine atom and the like can be mentioned.
• Examples of the alkoxy group represented by Y include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
• the acyloxy group represented by Y includes, for example, an acetoxy group, an ethylyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group, an n-hexanecarbonyloxy group, an n-octanecarbonyloxy group, and the like. can be done.
• Y is preferably an alkoxy group or an acyloxy group, more preferably an isopropoxy group or an acetoxy group.
• b is preferably 3 or 4, more preferably 4.
• metal-containing compound a metal alkoxide that is neither hydrolyzed nor hydrolytically condensed, and a metal acyloxide that is neither hydrolyzed nor hydrolytically condensed are preferable.
• Metal-containing compounds include zirconium tetra-n-butoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, hafnium tetraethoxide, indium triisopropoxide, and hafnium tetraisopropoxide.
• hafnium tetra-n-propoxide hafnium tetra-n-butoxide
• tantalum pentaethoxide tantalum penta-n-butoxide
• tungsten pentamethoxide tungsten penta-n-butoxide
• tungsten hexaethoxide tungsten Hexa-n-butoxide
• iron chloride zinc diisopropoxide, zinc acetate dihydrate, tetrabutyl orthotitanate
• titanium tri-n-butoxide stearate bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)tungsten dichloride, diacetato [(S)-(-)- 2,2′-bis(dip
• metal alkoxides and metal acyloxides are preferred, metal alkoxides are more preferred, and alkoxides of titanium, zirconium, hafnium, tantalum, tungsten and tin are more preferred.
• the lower limit of the amount of the organic acid used is preferably 1 mol, more preferably 2 mol, per 1 mol of the [b] metal-containing compound.
• the upper limit of the amount of the organic acid used is preferably 6 mol, more preferably 5 mol, per 1 mol of the metal-containing compound [b].
• a compound that can be a multidentate ligand represented by L in the compound of the above formula ( ⁇ ) and a bridging ligand A compound or the like that can become a ligand may be added.
• the compound that can be the bridging ligand include compounds having a plurality of hydroxy groups, isocyanate groups, amino groups, ester groups and amide groups.
• Examples of the [b] method of performing a hydrolysis-condensation reaction using a metal-containing compound include a method of subjecting a [b] metal-containing compound to a hydrolysis-condensation reaction in a solvent containing water. In this case, other compounds having hydrolyzable groups may be added as necessary.
• the lower limit of the amount of water used in this hydrolytic condensation reaction is preferably 0.2-fold mol, more preferably 1-fold mol, and 3-fold mol relative to the hydrolyzable group of the [b] metal-containing compound or the like. More preferred.
• the upper limit of the amount of water is preferably 20-fold mol, more preferably 15-fold mol, and still more preferably 10-fold mol.
• a method of performing a ligand exchange reaction using a metal-containing compound for example, a method of mixing [b] a metal-containing compound and [a] an organic acid can be mentioned.
• the mixture may be mixed in a solvent or may be mixed without using a solvent.
• a base such as triethylamine may be added as necessary.
• the amount of the base to be added is, for example, 1 part by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the total amount of the metal-containing compound [b] and the organic acid [a].
• the solvent used in the synthesis reaction of the compound (hereinafter also referred to as "[d] solvent”) is not particularly limited, and for example, the same solvents as those exemplified as the [B] solvent described later can be used. can.
• alcohol solvents, ether solvents, ester solvents and hydrocarbon solvents are preferred, alcohol solvents, ether solvents and ester solvents are more preferred, monoalcohol solvents and polyhydric alcohol partial ether solvents are preferred.
• Solvents such as polyhydric alcohol partial ether carboxylate solvents are more preferable, and monoalcohol solvents having 1 to 4 carbon atoms, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate are particularly preferable.
• the solvent used may be removed after the reaction.
• the [B] solvent is not particularly limited as long as it can dissolve or disperse at least the [A] compound and other optional components.
• the composition may contain one or more [B] solvents.
• solvents include organic solvents.
• organic solvents include alcohol solvents, ketone solvents, ether solvents, ester solvents, nitrogen-containing solvents, sulfur-containing solvents, and the like.
• alcoholic solvents examples include monoalcoholic solvents such as methanol, ethanol and n-propanol, and polyhydric alcoholic solvents such as ethylene glycol, 1,2-propylene glycol, triethylene glycol and tripropylene glycol. can be done.
• ketone solvents include chain ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and 2-heptanone, and cyclic ketone solvents such as cyclohexanone.
• ether solvents include chain ether solvents such as n-butyl ether, polyhydric alcohol ether solvents such as cyclic ether solvents such as tetrahydrofuran and 1,4-dioxane, propylene glycol monoethyl ether, and tripropylene glycol.
• chain ether solvents such as n-butyl ether
• polyhydric alcohol ether solvents such as cyclic ether solvents such as tetrahydrofuran and 1,4-dioxane
• propylene glycol monoethyl ether propylene glycol monoethyl ether
• tripropylene glycol examples include polyhydric alcohol partial ether solvents such as monomethyl ether and tetraethylene glycol monomethyl ether.
• ester solvents include carbonate solvents such as diethyl carbonate, acetic acid monoester solvents such as methyl acetate, ethyl acetate, and butyl acetate, lactone solvents such as ⁇ -butyrolactone, diethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether.
• Examples include polyhydric alcohol partial ether carboxylate solvents such as acetate, and lactate ester solvents such as methyl lactate and ethyl lactate.
• nitrogen-containing solvents examples include linear nitrogen-containing solvents such as N,N-dimethylacetamide and cyclic nitrogen-containing solvents such as N-methylpyrrolidone.
• sulfur-containing solvents examples include chain sulfur-containing solvents such as dimethylsulfone and dimethylsulfoxide, and cyclic sulfur-containing solvents such as sulfolane.
• aromatic solvents such as toluene, xylene, and mesitylene can be mentioned.
• the solvent is preferably an ether solvent, an ester solvent, a ketone solvent, or a combination thereof. ketone-based solvents or combinations thereof are more preferred, and propylene glycol monoethyl ether, butyl acetate, propylene glycol monomethyl ether acetate, 2-heptanone or combinations thereof are even more preferred.
• the lower limit of the content of [B] solvent in the total amount of [A] compound and [B] solvent is more preferably 50% by mass, preferably 60% by mass, and more preferably 70% by mass.
• the upper limit of the content is preferably 99% by mass, more preferably 95% by mass, and more preferably 90% by mass. [B] By setting the content of the solvent within the above range, it is possible to facilitate the preparation of the composition and to improve the coatability.
• composition may contain, for example, an acid generator, a polymer additive, a polymerization inhibitor, a surfactant, etc., as components other than those mentioned above.
• the content of the other optional ingredients in the composition can be appropriately determined according to the type and function of the other optional ingredients used.
• An acid generator is a compound that generates an acid upon exposure to radiation and/or heating.
• the composition can contain one or more acid generators.
• acid generators include onium salt compounds and N-sulfonyloxyimide compounds.
• the composition can further improve the coatability of the substrate and the organic underlayer film, as well as the continuity of the film.
• the composition may contain one or more polymeric additives.
• polymer additives examples include (poly)oxyalkylene polymer compounds, fluorine-containing polymer compounds, and non-fluorine polymer compounds.
• Examples of (poly)oxyalkylene-based polymer compounds include polyoxyalkylenes such as (poly)oxyethylene (poly)oxypropylene adducts, diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxy Ethylene polyoxypropylene-2-ethylhexyl ether, (poly)oxyalkyl ethers such as oxyethyleneoxypropylene adducts to higher alcohols having 12 to 14 carbon atoms, polyoxypropylene phenyl ether, polyoxyethylene nonylphenyl ether, etc.
• polyoxyalkylenes such as (poly)oxyethylene (poly)oxypropylene adducts, diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxy Ethylene polyoxypropylene-2-ethylhexyl ether, (pol
• (poly)oxyalkylene(alkyl)aryl ethers 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3 -Acetylene ethers obtained by addition polymerization of alkylene oxide to acetylene alcohol such as methyl-1-butyn-3-ol, (poly)oxyalkylene fatty acid esters such as diethylene glycol oleate, diethylene glycol laurate, and ethylene glycol distearate (poly)oxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan trioleate, etc., (poly) such as sodium polyoxypropylene methyl ether sulfate, sodium polyoxyethylene dodecylphenol ether sulfate ) Oxyalkylene alkyl (aryl) ether sulfate
• fluorine-containing polymer compounds examples include compounds described in JP-A-2011-89090.
• the fluorine-containing polymer compound for example, a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably an ethyleneoxy group or a propyleneoxy group). and a repeating unit derived from a (meth)acrylate compound having
• non-fluorinated polymer compounds include lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, isooctyl (meth)acrylate, isostearyl ( meth)acrylates, linear or branched alkyl (meth)acrylates such as isononyl (meth)acrylate, alkoxyethyl (meth)acrylates such as methoxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,3 - Alkylene glycol di(meth)acrylates such as butylene glycol di(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl ( Hydroxyalkyl (meth)acrylates such as meth)acrylates, dicyclopen
• the composition can improve the storage stability of the composition by containing a polymerization inhibitor.
• the composition can contain one or more polymerization inhibitors.
• polymerization inhibitors examples include hydroquinone compounds such as 4-methoxyphenol and 2,5-di-tert-butylhydroquinone, and nitroso compounds such as N-nitrosophenylhydroxylamine and aluminum salts thereof.
• the composition can further improve the coatability of the substrate and the organic underlayer film, as well as the continuity of the film.
• the composition can contain one or more surfactants.
• surfactants examples include “Newcol 2320”, “Newcol 714-F”, “Newcol 723”, “Newcol 2307”, “Newcol 2303” (Nippon Emulsifier Co., Ltd.), “Pionin D -1107-S”, “Pionin D-1007”, “Pionin D-1106-DIR”, “Nucalgen TG310”, “Nucalgen TG310”, “Pionin D-6105-W”, “Pionin D-6112", “Pionin D-6512” (above, Takemoto Oil Co., Ltd.), “Surfinol 420", “Surfinol 440", “Surfinol 465", “Surfinol 2502” (above, Japan Air Products Co., Ltd.), "Megafac F171", “F172”, “F173”, “F176”, “F177”, “F141”, “F142”, “F143”, “F144”, “R30” , "Same F4
• composition for forming a resist underlayer film is prepared by mixing the [A] compound, [B] solvent and optionally optional components in a predetermined ratio, and preferably filtering the obtained mixture through a membrane filter having a pore size of 0.5 ⁇ m or less. It can be prepared by filtering with
• the cleaning liquid contains [E] an organic acid.
• the cleaning liquid preferably further contains an organic solvent (hereinafter also referred to as "[G] organic solvent”).
• the cleaning liquid may contain water as a solvent other than the organic solvent.
• the cleaning liquid may contain other optional components as long as the effects of the present invention are not impaired. Examples of optional components include the components exemplified as the ligand represented by L in the above formula ( ⁇ ).
• [E] organic acid] are organic acids that are not polymeric. By adding the [E] organic acid to the cleaning liquid, the film formed on the periphery of the substrate can be easily removed.
• the lower limit of the molecular weight of the organic acid is preferably 45, more preferably 55, even more preferably 65, and particularly preferably 70, from the viewpoint of drainage stability.
• the upper limit of the molecular weight of the organic acid is preferably 500, more preferably 400, and even more preferably 300.
• Organic acids may be used alone or in combination of two or more. As the [E] organic acid, the [a] organic acid used for synthesizing the [A] compound can be suitably employed.
• a carboxylic acid is preferable. More specifically, for example, formic acid, acetic acid, propionic acid, butanoic acid (butyric acid), isobutanoic acid (isobutyric acid), pentanoic acid, hexanoic acid, 2-ethylhexanoic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, 1-adamantane
• Carboxylic acids consisting of aliphatic saturated hydrocarbon groups and/or aromatic hydrocarbon groups such as carboxylic acid, benzoic acid and phenylacetic acid and carboxy groups, fluorine atom-containing monocarboxylic acids such as difluoroacetic acid, trifluoroacetic acid, pentafluoropropanoic acid, heptafluorobutanoic acid, fluorophenylacetic acid, and difluorobenzoic acid; 10-hydroxydecanoic acid, 5-oxohexa
• the organic acid is preferably an unsaturated carboxylic acid, more preferably an unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, isocrotone, from the viewpoints of washability and drainage stability. More preferably, it is at least one selected from the group consisting of acids and 3-butenoic acid.
• the lower limit of the content of the [E] organic acid in all components contained in the cleaning solution is preferably 0.5% by mass, more preferably 1% by mass, even more preferably 2% by mass, and particularly 3 parts by mass. preferable.
• the upper limit of the content ratio is preferably 80% by mass, more preferably 70% by mass, still more preferably 65% by mass, and particularly preferably 60% by mass.
• [[G] organic solvent] As the [G] organic solvent suitably contained in the cleaning liquid, the above organic solvents exemplified as the [B] solvent contained in the composition for forming a resist underlayer film can be employed.
• the [G] organic solvent is preferably at least one selected from the group consisting of the ketone solvent and the ester solvent, the chain ketone solvent, the acetic acid monoester solvent, the polyhydric alcohol Partial ether carboxylate solvents or combinations thereof are more preferred, and butyl acetate, propylene glycol monomethyl ether acetate, 2-heptanone or combinations thereof are even more preferred.
• the lower limit of the content of the [G] organic solvent in the total amount of the [E] organic acid and [G] organic solvent is more preferably 20% by mass, preferably 30% by mass, and more preferably 35% by mass.
• the upper limit of the content is preferably 99% by mass, more preferably 98% by mass, and more preferably 95% by mass.
• the washing solution is prepared by mixing [E] an organic acid and optionally [G] an organic solvent and optional components in a predetermined ratio, and preferably filtering the resulting mixture through a membrane filter having a pore size of 0.5 ⁇ m or less.
• a membrane filter having a pore size of 0.5 ⁇ m or less.
• the composition for forming a resist underlayer film is directly or indirectly coated onto the substrate.
• the method of coating the composition for forming a resist underlayer film is not particularly limited, and can be carried out by an appropriate method such as spin coating, casting coating, roll coating, or the like. As a result, a coating film is formed, and [B] a resist underlayer film is formed by volatilization of the solvent.
• the substrate examples include metal or semimetal substrates such as silicon substrates, aluminum substrates, nickel substrates, chromium substrates, molybdenum substrates, tungsten substrates, copper substrates, tantalum substrates, and titanium substrates.
• metal or semimetal substrates such as silicon substrates, aluminum substrates, nickel substrates, chromium substrates, molybdenum substrates, tungsten substrates, copper substrates, tantalum substrates, and titanium substrates.
• silicon substrates are preferred.
• 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 lower limit to the average thickness of the resist underlayer film to be formed is preferably 3 nm, more preferably 5 nm, and even more preferably 10 nm.
• the upper limit of the average thickness is preferably 500 nm, more preferably 200 nm, and even more preferably 60 nm. The method for measuring the average thickness is described in Examples.
• the method for manufacturing the semiconductor substrate preferably further includes a step of heating the coating film formed by the coating step (hereinafter also referred to as a "heating step").
• the heating of the coating promotes the formation of the resist underlayer film. More specifically, heating the coating film promotes volatilization of the [B] solvent.
• the heating of the coating film is usually performed in the air, but may be performed in a nitrogen atmosphere.
• the lower limit of the heating temperature is preferably 150°C, more preferably 200°C.
• the upper limit of the temperature is preferably 600°C, more preferably 500°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 organic underlayer film can be formed by coating a composition for forming an organic underlayer film.
• the method of forming the organic underlayer film by coating the composition for forming an organic underlayer film includes, for example, coating the composition for forming an organic underlayer film directly or indirectly on a substrate having the resist underlayer film. A method of curing the coating film by heating or exposing it to light can be mentioned.
• the composition for forming the organic underlayer film for example, "HM8006" manufactured by JSR Corporation can be used. Various conditions for heating and exposure can be appropriately determined according to the type of the organic underlayer film-forming composition to be used.
• Silicon-containing film forming step In this step, prior to the resist pattern forming step, a silicon-containing film is formed directly or indirectly on the substrate having the resist underlayer film formed in the coating step.
• Examples of the case of indirectly forming a silicon-containing film on a substrate having the resist underlayer film include, for example, the case where a surface modification film of the resist underlayer film is formed on the resist underlayer film.
• a silicon-containing film can be formed by coating a composition for forming a silicon-containing film, chemical vapor deposition (CVD), atomic layer deposition (ALD), or the like.
• CVD chemical vapor deposition
• ALD atomic layer deposition
• a method of forming a silicon-containing film by coating a composition for forming a silicon-containing film for example, a coating formed by directly or indirectly coating a composition for forming a silicon-containing film on the resist underlayer film.
• a method of curing the coating film by exposure and/or heating can be mentioned.
• Commercially available products of the silicon-containing film-forming composition include, for example, "NFC SOG01", “NFC SOG04", and "NFC SOG080" (manufactured by JSR Corporation).
• Silicon oxide films, silicon nitride films, silicon oxynitride films, and amorphous silicon films can be formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD).
• the periphery of the substrate is cleaned with a cleaning liquid.
• the cleaning liquid can be preferably used.
• the washing method is not particularly limited, and a known method can be adopted. Typically, first, a substrate on which various films are formed is rotated at a predetermined speed. Next, while discharging the cleaning liquid from the cleaning liquid discharge nozzle, the cleaning liquid discharge nozzle is moved at a predetermined speed from the outer peripheral edge of the rotating substrate toward the center of the substrate. When the cleaning liquid discharge nozzle moves a predetermined distance, the movement is stopped, and the cleaning liquid is discharged for a predetermined time. After that, the cleaning is completed by stopping the ejection of the cleaning liquid from the cleaning liquid ejection nozzle, and drying it if necessary.
• the rotation speed of the substrate, the amount of cleaning liquid discharged per unit time, the moving speed and moving distance of the cleaning liquid discharging nozzle, the cleaning liquid discharging time after stopping the movement of the cleaning liquid discharging nozzle, etc. are all dependent on the size of the substrate, the number of films formed, It may be appropriately set according to the type, thickness, cleaning area, and the like.
• a cleaning step can be performed with or without the heating step.
• the heating step is preferably performed after the washing step.
• resist pattern forming step In this step, after the cleaning step, a resist pattern is formed directly or indirectly on the resist underlayer film.
• the method for carrying out this step include a method using a resist composition, a method using a nanoimprint method, a method using a self-assembled composition, and the like.
• Examples of forming a resist pattern indirectly on the resist underlayer film include, for example, forming a resist pattern on the silicon-containing film in the case where the method for manufacturing the semiconductor substrate includes the step of forming the silicon-containing film. I can give
• the method using the above resist composition is performed by coating the resist composition so that the resist film to be formed has a predetermined thickness, and then pre-baking if necessary to remove the solvent in the coating film. is volatilized to form a resist film.
• the resist composition examples include a positive or negative chemically amplified resist composition containing a radiation-sensitive acid generator, a positive resist composition containing an alkali-soluble resin and a quinonediazide-based photosensitizer, an alkali A negative resist composition containing a soluble resin and a cross-linking agent can be mentioned.
• a commercially available resist composition can be used as it is.
• the radiation used for exposure can be appropriately selected according to the type of radiation-sensitive acid generator used in the resist composition.
• Examples include electromagnetic waves, electron beams, molecular beams, and particle beams such as ion beams.
• far ultraviolet rays are preferred, 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.
• extreme ultraviolet rays wavelength of 13.5 nm, etc., hereinafter also referred to as "EUV" are more preferred, and KrF excimer laser light, ArF excimer laser light, or EUV is even more preferred.
• post-baking can be performed to improve the resolution, pattern profile, developability, and the like.
• the temperature and time of this post-baking can be appropriately determined according to the type of resist composition used.
• the exposed resist film is developed with a developer to form a resist pattern.
• This development may be either alkali development or organic solvent development.
• the developer in the case of alkali development, basic aqueous solutions such as ammonia, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide and the like can be used. Suitable amounts of water-soluble organic solvents such as alcohols such as methanol and ethanol, surfactants and the like can also be added to these basic aqueous solutions.
• examples of the developer include various organic solvents exemplified as the [B] solvent of the composition.
• a predetermined resist pattern is formed by washing and drying after development with the developer.
• a pattern is formed in the resist underlayer film by etching using the resist pattern as a mask.
• Etching may be performed once or multiple times, that is, etching may be performed sequentially using the pattern obtained by etching as a mask, but multiple times is preferable from the viewpoint of obtaining a pattern with a better shape.
• the silicon-containing film, the organic underlayer film, the resist underlayer film, and the substrate are sequentially etched in this order.
• the etching method dry etching, wet etching, and the like can be mentioned. Among these, dry etching is preferable from the viewpoint of improving the pattern shape of the substrate.
• gas plasma such as oxygen plasma is used.
• a semiconductor substrate having a predetermined pattern is obtained by the etching.
• 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, etc. Examples include CHF 3 , CF 4 , C 2 F 6 , C 3 F 8 , SF 6 and the like.
• chlorine-based gases such as Cl 2 and BCl 3 ; oxygen-based gases such as O 2 , O 3 and H 2 O; H 2 , NH 3 , CO, CO 2 , CH 4 and C 2 H 2 ; Reducing gases such as C2H4 , C2H6 , C3H4 , C3H6 , C3H8 , HF , HI, HBr, HCl and NO , inert gases such as He, N2 and Ar You can give gas. These gases can also be mixed and used. When etching a substrate using the pattern of the resist underlayer film as a mask, a fluorine-based gas is usually used.
• the method for forming the resist underlayer film includes a step of directly or indirectly coating a substrate with a composition for forming a resist underlayer film.
• a composition for forming a resist underlayer film the composition for forming a resist underlayer film used in the method for manufacturing a semiconductor substrate can be suitably employed.
• the coating step the coating step in the above method for manufacturing a semiconductor substrate can be suitably employed.
• the cleaning liquid contains [E] an organic acid. Furthermore, the cleaning liquid preferably contains an organic solvent.
• the cleaning liquid may contain water as a solvent other than the organic solvent. As such a cleaning liquid, the cleaning liquid used in the above method for manufacturing a semiconductor substrate can be preferably adopted.
• the concentration of components other than the solvent in the mixture containing the [A] compound in the present example, the weight average molecular weight (Mw) of the hydrolysis condensation product in the mixture containing the [A] compound, and the average thickness of the film were determined by the following methods. It was measured.
• the average thickness of the resist underlayer film is determined by measuring the film thickness at arbitrary 9 points at intervals of 5 cm including the center of the resist underlayer film using a spectroscopic ellipsometer ("M2000D" manufactured by JA WOOLLAM). It was obtained by calculating the average value of the film thickness of .
• x-1 propionic acid
• x-2 butyric acid
• x-3 isobutyric acid
• x-4 methacrylic acid
• x-5 2-ethylhexanoic acid
• x-6 acetylacetone
• x-7 diethanolamine
• B-1 Propylene glycol monomethyl ether acetate
• B-2 Propylene glycol monoethyl ether
• composition (J-1) As shown in Table 2 below, (B-3 ) was mixed so as to be 90 parts by mass. The resulting solution was filtered through a polytetrafluoroethylene (PTFE) filter with a pore size of 0.2 ⁇ m to prepare composition (J-1). "-" in [F] and other optional ingredients in Table 2 below indicates that [F] and other optional ingredients were not used. The same applies hereinafter.
• PTFE polytetrafluoroethylene
• composition (J-2) As shown in Table 2 below, [A] a mixture containing compound (A-2) and [B] (B-1) as a solvent , with respect to 10 parts by mass of components other than the solvent in the [A] compound (A-2), 90 parts by mass of the solvent [B] (including the [B] solvent contained in the mixture containing the [A] compound) and mixed so that The resulting solution was filtered through a polytetrafluoroethylene (PTFE) filter with a pore size of 0.2 ⁇ m to prepare composition (J-2).
• PTFE polytetrafluoroethylene
• compositions (J-3) to (J-29) were prepared in the same manner as in Example 1-2.
• "-" in Table 2 below indicates that the corresponding component was not used.
• E As organic acids, the following compounds (E-1) to (E-10) were used.
• G as an organic solvent
• the following compounds (G-1) to (G-4) and (G-6) to (G-7), [G] as a solvent other than the organic solvent (G-5) were used respectively.
• G-1 propylene glycol monomethyl ether acetate
• G-2 butyl acetate
• G-3 2-heptanone
• G-4 propylene glycol monomethyl ether
• G-5 water
• G-6 dimethyl sulfoxide
• G-7 sulfolane
• Example 2-1 Preparation of cleaning liquid (K-1) As shown in Table 3 below, (E) as an organic acid (E- 1) was mixed so as to be 20 parts by mass. The obtained solution was filtered through a polytetrafluoroethylene (PTFE) filter with a pore size of 0.2 ⁇ m to prepare a cleaning solution (K-1). "-" in Table 3 below indicates that the corresponding component was not used.
• PTFE polytetrafluoroethylene
• Example 2-2 to 2-29 and Comparative Example 1-1 Preparation of cleaning solutions (K-2) to (K-29) and (k-1) The types and contents of each component are shown in Table 3 below. Cleaning solutions (K-2) to (K-29) and (k-1) were prepared in the same manner as in Example 2-1, except that
• Each composition prepared above was coated on a silicon wafer (substrate) using a spin coater ("CLEAN TRACK ACT8" available from Tokyo Electron Co., Ltd.) by a spin coating method. While moving the cleaning liquid ejection nozzle at a speed of 1 mm per second, the cleaning liquid (K) is ejected at a rate of 2 ml per second to a position where the length from the outer peripheral edge of the substrate to the center of the substrate is 2 mm. After the cleaning liquid was discharged at a rate of 2 ml per second for 10 seconds at a position where the length from the outer peripheral edge of the substrate to the center of the substrate was 2 mm, the substrate was rotated at 1,500 rpm for 30 seconds.
• a spin coater (“CLEAN TRACK ACT8" available from Tokyo Electron Co., Ltd.)
• this substrate was heated at 450° C. for 60 seconds to obtain an evaluation substrate A with a resist underlayer film having an average thickness of 30 nm.
• the outermost surface of the obtained evaluation substrate A front and back areas 0.3 mm from the edge
• was wetted with an acid was wetted with an acid, and the entire amount of the liquid obtained by the wettability was collected and used as a measurement test liquid, and inductive coupling was performed.
• the amount of metal was measured by plasma mass spectrometry (ICP-MS).
• An evaluation substrate B with a resist underlayer film having an average thickness of 30 nm was obtained in the same manner as the procedure for obtaining the evaluation substrate A, except that the cleaning liquid (k-1) was used as the cleaning liquid.
• the outermost surface of the obtained evaluation substrate B (front and back areas 0.3 mm from the edge) was wetted with an acid, and the entire amount of the liquid obtained by the wettability was collected and used as a measurement test liquid, and inductive coupling was performed.
• the amount of metal was measured by plasma mass spectrometry (ICP-MS).
• the metal detergency is "A" when the amount of metal constituting the [A] compound detected from the evaluation substrate A is less than 10% compared to the evaluation substrate B, and when it is 10% or more and less than 50%. It was evaluated as “B”, and in the case of 50% or more, it was evaluated as "C”.
• [Drainage stability] A mixed solution was prepared by mixing equal amounts of the composition (J) and the cleaning solution (K), and the mixture was allowed to stand at 23° C. and ⁇ 15° C. for one week, and the presence or absence of precipitation and turbidity was visually observed. Effluent stability was evaluated as "A" when there was no precipitation or turbidity after standing the mixed solution prepared at -15 ° C. for one week, and there was no precipitation or turbidity after standing at 23 ° C. for one week. If there was precipitation or turbidity after standing at -15°C for one week, it was evaluated as "B".
• the peripheral portion of the substrate is cleaned using a cleaning liquid having excellent cleaning properties and excellent drainage stability, so that high-quality semiconductor substrates can be efficiently manufactured.
• a cleaning liquid excellent in cleaning properties and drainage stability is used.
• the cleaning liquid of the present invention is excellent in both detergency and drainage stability. Therefore, these can be suitably used for the manufacture of semiconductor devices, etc., which are expected to be further miniaturized in the future.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Emergency Medicine (AREA)
• Health & Medical Sciences (AREA)
• Architecture (AREA)
• Structural Engineering (AREA)
• Metallurgy (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Cleaning Or Drying Semiconductors (AREA)
• Materials For Photolithography (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=87279192

Family Applications (1)

Country Status (6)

Citations (10)

Family Cites Families (1)

• 2023
  • 2023-01-11 JP JP2023574046A patent/JPWO2023136260A1/ja active Pending
  • 2023-01-11 WO PCT/JP2023/000437 patent/WO2023136260A1/ja not_active Ceased
  • 2023-01-11 CN CN202380015443.5A patent/CN118435121A/zh active Pending
  • 2023-01-11 KR KR1020247023031A patent/KR20240137561A/ko active Pending
  • 2023-01-13 TW TW112101609A patent/TW202331416A/zh unknown
• 2024
  • 2024-07-11 US US18/769,554 patent/US20240369931A1/en active Pending

Patent Citations (10)

Also Published As

Similar Documents

Legal Events