WO2017126554A1 - Solution de traitement - Google Patents

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Publication number
WO2017126554A1
WO2017126554A1 PCT/JP2017/001560 JP2017001560W WO2017126554A1 WO 2017126554 A1 WO2017126554 A1 WO 2017126554A1 JP 2017001560 W JP2017001560 W JP 2017001560W WO 2017126554 A1 WO2017126554 A1 WO 2017126554A1
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Prior art keywords
treatment liquid
mass
substrate
acid
film
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PCT/JP2017/001560
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English (en)
Japanese (ja)
Inventor
哲 村山
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2017562852A priority Critical patent/JP6646073B2/ja
Priority to KR1020187018406A priority patent/KR102113463B1/ko
Publication of WO2017126554A1 publication Critical patent/WO2017126554A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/08—Liquid soap, e.g. for dispensers; capsuled
    • 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
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/08—Acids
    • 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
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • 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
    • C11D7/32—Organic compounds containing nitrogen
    • 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
    • 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
    • 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 processing liquid mainly applied to processing of a semiconductor device substrate.
  • a lithography process using a positive-type or negative-type photoresist is employed.
  • a photoresist film coated on a substrate (for example, a silicon substrate and a substrate on which a circuit structure is formed) is exposed through an exposure master such as a photomask.
  • an exposure master such as a photomask.
  • a resist resist pattern, resist film
  • Etching is performed using the obtained resist as a mask.
  • the wet method using a stripping solution is a form in which a resist used as a mask at the time of etching is stripped and removed using a treatment solution (stripping composition).
  • a permanent film for example, a pattern film such as a color filter
  • the permanent film is required to be removed.
  • the permanent film is removed from the entire substrate and the substrate is reused (regenerated).
  • examples of the permanent film include a finely processed color filter, a transparent insulating film, and a resin lens, which are applied to manufacture of a solid-state imaging device and an image display device.
  • removing the permanent film as in the case of the resist used as a mask at the time of etching as described above, it is considered to remove and remove using a stripping composition as a treatment liquid.
  • Patent Document 1 discloses a cleaning composition for removing a color resist as a permanent film removing solution. More specifically, a cleaning composition containing tetramethylammonium hydroxide (TMAH) is disclosed.
  • TMAH tetramethylammonium hydroxide
  • the present inventor uses the removing liquid described in Patent Document 1 to remove and remove organic films (for example, various resists and permanent films used as a mask during etching) on the substrate, and dry etching residue.
  • organic films for example, various resists and permanent films used as a mask during etching
  • the removal liquid described in Patent Document 1 does not satisfy the desired requirements and needs further improvement. became.
  • metal such as an electrode or wiring disposed on the substrate Often the film is exposed.
  • the treatment liquid needs to have corrosion resistance to metal films (particularly aluminum films) such as electrodes or wirings formed on the substrate.
  • the present invention has a corrosion prevention property for the metal film disposed on the substrate, and a removal property for the organic film on the substrate, or a removal for dry etching residue or dry ashing residue adhered on the substrate. It aims at providing the processing liquid which is excellent in property.
  • the present inventor has found that water, a hydrophilic organic solvent, a quaternary ammonium salt, a predetermined amount (0.001 mass ppt to 1 mass ppm relative to the total mass of the treatment liquid). It was found that a desired effect can be obtained by using a treatment liquid containing an inorganic anion). That is, it has been found that the above object can be achieved by the following configuration.
  • a treatment liquid containing water, a hydrophilic organic solvent, a quaternary ammonium salt, and an inorganic anion A treatment liquid, wherein the content of the inorganic anion is 0.001 mass ppt to 1 mass ppm relative to the total mass of the treatment liquid.
  • the water content is 1-30% by mass, The content of the hydrophilic organic solvent is 40 to 98% by mass, The treatment liquid according to any one of (1) to (3), wherein the content of the quaternary ammonium salt is 0.1 to 30% by mass.
  • the water content is 20 to 98% by mass, The content of the hydrophilic organic solvent is 1 to 40% by mass, The treatment liquid according to any one of (1) to (3), wherein the content of the quaternary ammonium salt is 0.1 to 30% by mass.
  • the metal film disposed on the substrate has corrosion resistance and can be removed from the organic film on the substrate, or removed from the dry etching residue or dry ashing residue attached on the substrate. It is possible to provide a treatment liquid having excellent properties.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the description that does not indicate substitution and non-substitution includes those that do not have a substituent and those that have a substituent, as long as the effects of the present invention are not impaired.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). This is synonymous also about each compound.
  • radiation in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
  • light means an actinic ray or radiation.
  • exposure in the present specification is not limited to exposure to deep ultraviolet rays such as mercury lamps and excimer lasers, X-rays and EUV light, but also particles such as electron beams and ion beams. Line drawing is also included in the exposure.
  • (meth) acrylate represents both and / or acrylate and methacrylate
  • (meth) acryl represents both and / or acryl and methacryl.
  • “monomer” and “monomer” are synonymous.
  • a monomer in the present specification is distinguished from an oligomer and a polymer, and unless otherwise specified, refers to a compound having a weight average molecular weight of 2,000 or less.
  • the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer.
  • the polymerizable functional group refers to a group that participates in a polymerization reaction.
  • the term “preparation” in the present specification means that a specific material is synthesized or blended, and a predetermined item is procured by purchase or the like.
  • the dry etching residue is a by-product generated by performing dry etching (for example, plasma etching), for example, a resist-derived organic residue, a Si-containing residue, and a metal-containing residue.
  • dry ash residue is a by-product generated by performing dry ashing (for example, plasma ashing), for example, a resist-derived organic residue, Si-containing residue, and This refers to metal-containing residues.
  • dry etching residue and dry ashing residue may be collectively referred to as “residue”.
  • the treatment liquid of the present invention contains water, a hydrophilic organic solvent, a quaternary ammonium salt, and an inorganic anion.
  • a feature of the present invention is that the content of inorganic anions in the treatment liquid having the above composition is 0.001 mass ppt to 1 mass ppm with respect to the total mass of the treatment liquid.
  • the inorganic anion preferably uses an inorganic acid as an ion source.
  • the treatment liquid of the present invention has the above-described configuration, so that it has corrosion resistance to the metal film disposed on the substrate, while it can be removed from the organic film on the substrate, or dry etching residue adhering to the substrate.
  • the treatment liquid can be used to remove a permanent film formed on a substrate or to remove and remove various resists used as a mask during etching, or to clean and remove dry etching residue or dry ashing residue adhered on the substrate. It is preferable to be used for.
  • each component contained in the treatment liquid of the present invention will be described, and then the method for producing the treatment liquid of the present invention will be described.
  • the treatment liquid of the present invention contains water as a solvent.
  • the water content is not particularly limited, but may be 1 to 99.999 mass% with respect to the total mass of the treatment liquid.
  • the treatment liquid of the present invention may be formulated as either an aqueous treatment liquid or an organic solvent treatment liquid by adjusting the contents of the hydrophilic organic solvent and water.
  • As the water ultrapure water used for semiconductor production is preferable, but it is more preferable to use water that is further purified to reduce inorganic anions and metal ions.
  • the purification method is not particularly limited, but purification using a filtration membrane or an ion exchange membrane, or purification by distillation is preferable.
  • the treatment liquid of the present invention contains a hydrophilic organic solvent.
  • a hydrophilic organic solvent By containing the hydrophilic organic solvent, it is possible to promote solubilization of the additive components and unnecessary organic substances and residues, and to further improve the corrosion prevention effect.
  • the hydrophilic organic solvent is preferably an organic solvent that can be uniformly mixed with water at any ratio.
  • hydrophilic organic solvent for example, water-soluble alcohol solvent, water-soluble ketone solvent, water-soluble ester solvent, water-soluble ether solvent (for example, glycol diether), sulfone solvent, sulfoxide
  • water-soluble alcohol solvent for example, water-soluble ketone solvent, water-soluble ester solvent, water-soluble ether solvent (for example, glycol diether), sulfone solvent, sulfoxide
  • sulfone solvent for example, glycol diether
  • sulfoxide examples thereof include a system solvent, a nitrile solvent, and an amide solvent, and any of these can be used to obtain the desired effect of the present application.
  • water-soluble alcohol solvent examples include alkanediol (for example, including alkylene glycol), alkoxy alcohol (for example, including glycol monoether), saturated aliphatic monohydric alcohol, unsaturated non-aromatic monohydric alcohol, and And low molecular weight alcohols containing a ring structure.
  • alkanediol examples include glycol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-diol, 1,4-butanediol, 1,3- Examples include butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, and alkylene glycol.
  • alkylene glycol examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol.
  • alkoxy alcohol examples include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, and glycol monoether.
  • glycol monoether examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol.
  • Monobutyl ether triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy- 1-propanol, propylene glycol mono-n-propyl ether , Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobenzyl ether, and diethylene glycol monobenzyl ether It is done.
  • saturated aliphatic monohydric alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, t-pentyl alcohol, and 1-hexanol is mentioned.
  • Examples of the unsaturated non-aromatic monohydric alcohol include allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, and 4-penten-2-ol.
  • Examples of the low molecular weight alcohol containing a ring structure include tetrahydrofurfuryl alcohol, furfuryl alcohol, and 1,3-cyclopentanediol.
  • water-soluble ketone solvents include acetone, propanone, cyclobutanone, cyclopentanone, cyclohexanone, diacetone alcohol, 2-butanone, 5-hexanedione, 1,4-cyclohexanedione, 3-hydroxyacetophenone, 1,3 -Cyclohexanedione and cyclohexanone.
  • water-soluble ester solvents examples include glycol monoesters such as ethyl acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, and propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, And glycol monoether monoesters such as ethylene glycol monoethyl ether acetate.
  • sulfone solvent examples include sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane, and the like.
  • sulfoxide solvent examples include dimethyl sulfoxide and the like.
  • a sulfoxide-based solvent it is preferable to use a grade in which inorganic ions such as sulfate ion, chloride ion or nitrate ion and metal ions described later are reduced, or further refined and used.
  • nitrile solvents examples include acetonitrile.
  • amide solvents include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ⁇ -caprolactam, formamide, and N-methyl.
  • Examples include formamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, and hexamethylphosphoric triamide.
  • hydrophilic organic solvents from the viewpoint of further improving the corrosion prevention effect, water-soluble alcohol solvents, sulfone solvents, amide solvents, and sulfoxide solvents are preferred, and water-soluble alcohol solvents and sulfoxide solvents are preferred.
  • a solvent is more preferable, and among these, ethylene glycol monobutyl ether, tri (propylene glycol) methyl ether, and diethylene glycol monoethyl ether are still more preferable. These are preferably used in grades in which inorganic ions such as sulfate ions, chloride ions, and nitrate ions, and metal ions described later are reduced, or further purified.
  • the hydrophilic organic solvents may be used alone or in appropriate combination of two or more.
  • the content of the hydrophilic organic solvent is not particularly limited, but may be 1 to 99.999% by mass with respect to the total mass of the treatment liquid.
  • the treatment liquid of the present invention can be made to have both liquid and organic solvent formulations by adjusting the contents of water and the hydrophilic organic solvent contained in the treatment liquid.
  • Aqueous processing solution When the aqueous treatment liquid is used, the water content is preferably 20 to 98% by mass, more preferably 35 to 98% by mass, and more preferably 50 to 95% by mass with respect to the total mass of the treatment liquid. More preferably. Further, the content of the hydrophilic organic solvent is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, and more preferably 10 to 30% by mass with respect to the total mass of the treatment liquid. More preferably.
  • the water content is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, more preferably 4 to 20%, based on the total mass of the treatment liquid. It is more preferable to set it as the mass%.
  • the content of the hydrophilic organic solvent is preferably 40 to 98% by mass, more preferably 45 to 98% by mass, and more preferably 50 to 95% by mass with respect to the total mass of the treatment liquid. More preferably.
  • the treatment liquid of the present invention contains a quaternary ammonium salt.
  • a quaternary ammonium salt By adding a quaternary ammonium salt, it is possible to further improve the removability to organic films (various resists, permanent films) and residues on the substrate.
  • the quaternary ammonium salt also functions as a pH adjuster.
  • the quaternary ammonium salt is preferably a compound represented by the following general formula (1).
  • R 4A to R 4D each independently represents an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a benzyl group, or an aryl group.
  • X ⁇ represents a counter anion. Represents.
  • R 4A to R 4D each independently represent an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, and a butyl group), or a hydroxyalkyl group having 1 to 6 carbon atoms (for example, , A hydroxymethyl group, a hydroxyethyl group, and a hydroxybutyl group), a benzyl group, or an aryl group (for example, a phenyl group, a naphthyl group, and a naphthalene group).
  • an alkyl group, a hydroxyethyl group, or a benzyl group is preferable.
  • X ⁇ represents a counter anion and is not particularly limited.
  • various acid anions such as carboxylate ions, phosphate ions, sulfate ions, phosphonate ions, and nitrate ions, and hydroxides Ions, halide ions (eg, chloride ions, fluoride ions, bromide ions, etc.) and the like.
  • Specific examples of the compound represented by the formula (1) include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, dimethyldi (hydroxyethyl) ammonium hydroxide, methyltrimethyl. (Hydroxyethyl) ammonium hydroxide, tetra (hydroxyethyl) ammonium hydroxide, benzyltrimethylammonium hydroxide, and choline.
  • Quaternary ammonium salts may be used alone or in combination of two or more.
  • the content of the quaternary ammonium salt in the treatment liquid is not particularly limited, but is preferably 0.1 to 30% by mass, and preferably 0.5 to 10% by mass with respect to the total mass of the treatment liquid. Is more preferably 0.5 to 5% by mass.
  • the treatment liquid of the present invention contains inorganic anions.
  • inorganic anions By containing a predetermined amount of inorganic anions in the treatment liquid, it is possible to further improve the removability of the organic film and residue on the substrate without corroding the metal film such as the electrode or wiring disposed on the substrate. it can.
  • a nitrate ion, a chloride ion, or a sulfate ion is preferable, and a nitrate ion is more preferable.
  • the treatment liquid may contain two or more inorganic anions.
  • the inorganic anion is preferably an inorganic acid ion source.
  • Examples of the method of adding an inorganic anion to the treatment liquid include a method of adding an inorganic acid such as nitric acid, hydrochloric acid or sulfuric acid to the treatment liquid.
  • examples of inorganic acids include nitric acid, hydrochloric acid, sulfuric acid, and phosphoric acid.
  • the content of the inorganic anion is 0.001 mass ppt to 1 mass ppm, preferably 0.001 mass ppt to 0.75 mass ppm with respect to the total mass of the treatment liquid, and 1 mass ppt to 0.75 mass ppm. Is more preferable, and 1 mass ppt to 0.5 mass ppm is even more preferable.
  • nitrate ions When two or more kinds of inorganic anions are contained in the treatment liquid, it is preferable that at least nitrate ions are contained and the amount of nitrate ions is in the above range.
  • a process liquid contains at least nitrate ion and sulfate ion, and each quantity of nitrate ion and sulfate ion is the said range, and a process liquid is nitrate ion, chloride ion,
  • at least sulfate ions are contained, and the respective amounts of nitrate ions, chloride ions, and sulfate ions are in the above range.
  • the treatment liquid contains at least one inorganic anion selected from nitrate ions, chloride ions, and sulfate ions
  • the treatment liquid further includes at least one selected from nitrate ions, chloride ions, and sulfate ions.
  • Content ratio (mass ratio) of the content of ionic species of each species (the amount of each of nitrate ions, chloride ions, and sulfate ions when two or more are included) and the content of the quaternary ammonium salt Is preferably adjusted to the following range.
  • the content of the quaternary ammonium salt is the content of at least one ion species selected from nitrate ions, chloride ions, and sulfate ions (two or more of nitrate ions, chloride ions, and sulfate ions are included).
  • the mass ratio is preferably 1 ⁇ 10 2 to 1 ⁇ 10 14 , more preferably 1 ⁇ 10 4 to 1 ⁇ 10 13, and more preferably 1 ⁇ 10 7. preferably more than to a ⁇ 1 ⁇ 10 12, it is particularly preferable to 1 ⁇ 10 9 ⁇ 1 ⁇ 10 12.
  • the treatment liquid of the present invention can not only keep the above-described effects of the present invention well even after aging, but also has excellent recyclability. It has been confirmed that The effect is particularly remarkable with nitrate ions and sulfate ions. During recycling, if washing is repeated, trace amounts of inorganic anions and metal-derived ions are eluted in the processing solution. Although the effects of the present invention may change depending on the accumulation thereof, it has been found that the recyclability is excellent within the above range. It is presumed that nitrate ions, chloride ions, and sulfate ions are particularly likely to interact with quaternary ammonium salts compared to other inorganic anions.
  • the content of the inorganic anion contained in the treatment liquid of the present invention can be adjusted by a known method.
  • a cation exchange resin, an anion exchange resin, or It can be reduced by passing through a purification apparatus comprising a mixed bed type ion exchange resin and performing secondary purification.
  • a method described in Japanese Patent Application Laid-Open No. 2007-254168 can also be used.
  • the step of reducing the content of the inorganic anion as described above is not particularly limited as long as the inorganic anion finally contained in the treatment liquid can be reduced.
  • an embodiment performed on a compound used in the treatment liquid for example, any solvent selected from water and a hydrophilic organic solvent
  • the aspect performed with respect to a process liquid may be sufficient.
  • an embodiment in which the compound used for the treatment liquid is performed before the treatment liquid is prepared is preferable.
  • Quantification of inorganic anions contained in the treatment liquid or water and solvents used in the treatment liquid can be analyzed by ion chromatography.
  • the analysis and measurement are preferably all performed in a clean room.
  • the clean room preferably meets the 14644-1 clean room criteria. It is preferable to satisfy any of ISO class 1, ISO class 2, ISO class 3, and ISO class 4, preferably ISO class 1 and ISO class 2, and particularly preferably ISO class 1.
  • the treatment liquid of the present invention preferably contains a corrosion inhibitor.
  • the corrosion inhibitor has a function of eliminating over-etching of a metal (for example, Co, W) that becomes a wiring film.
  • the corrosion inhibitor is not particularly limited.
  • 1,2,4-triazole TEZ
  • 5-aminotetrazole ATA
  • 5-amino-1,3,4-thiadiazole-2-thiol 3-amino -1H-1,2,4 triazole
  • 3,5-diamino-1,2,4-triazole tolyltriazole
  • 3-amino-5-mercapto-1,2,4-triazole 1-amino-1,2 , 4-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1 , 2,4-triazole, naphthotriazole, 1H-tetrazole-5-acetic acid, 2-mercaptobenzothiazole (2-MBT), 1-phenyl-2-tetrazoli -5-thione, 2-mercaptobenzimidazole (2-MBI), 4-methyl-2-phenylimidazole, 2-mercaptothiazo
  • the substituted benzotriazole is preferably, for example, an benzotriazole substituted with an alkyl group, an aryl group, a halogen group, an amino group, a nitro group, an alkoxy group, or a hydroxyl group.
  • the substituted bebenzotriazole may be condensed with one or more aryl (eg, phenyl) or heteroaryl groups.
  • the substituted or unsubstituted benzotriazole includes, in addition to those described above, benzotriazole (BTA), 5-aminotetrazole, 1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole Triazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthotriazole, tolyltriazole, 5-phenyl-benzotriazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole 3-amino-5-mercapto-1,2,4-triazole, 2- (5-amino-pentyl) -benzotriazole, 1-amino-benzotriazole, 5-methyl-1H-benzo Riazole, benzotriazole-5-carboxylic acid, 4-methylbenzotriazole, 4-ethylbenzotriazo
  • the corrosion inhibitor is preferably any one selected from compounds represented by the following formulas (A) to (C) and substituted or unsubstituted tetrazole from the viewpoint of further improving the corrosion resistance. .
  • R 1A to R 5A each independently represents a hydrogen atom, a substituent or an unsubstituted hydrocarbon group, a hydroxyl group, a carboxy group, or a substituted or unsubstituted amino group. However, the structure contains at least one group selected from a hydroxyl group, a carboxy group, and a substituted or unsubstituted amino group.
  • R 1B to R 4B each independently represents a hydrogen atom, a substituent, or an unsubstituted hydrocarbon group.
  • R 1C, R 2C and R N are each independently represent a hydrogen atom, a substituent or unsubstituted hydrocarbon group. R 1C and R 2C may be bonded to form a ring.
  • the hydrocarbon represented by R 1A to R 5A is an alkyl group (the carbon number is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), an alkenyl group ( The number of carbon atoms is preferably 2-12, more preferably 2-6, an alkynyl group (carbon number is preferably 2-12, more preferably 2-6), and an aryl group (carbon number is 6-22). 6 to 14 are more preferable, and 6 to 10 are particularly preferable.) And aralkyl groups (the carbon number is preferably 7 to 23, more preferably 7 to 15, and particularly preferably 7 to 11).
  • substituents examples include a hydroxyl group, a carboxy group, or a substituted or unsubstituted amino group (the substituent is preferably an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 3 carbon atoms). Is more preferable).
  • a hydroxyl group, a carboxy group, and a substituted or unsubstituted amino group in the structure (the substituent is preferably an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 3 carbon atoms). At least one group selected from the group (which is more preferable).
  • examples of the substituent or unsubstituted hydrocarbon group represented by R 1A to R 5A include an unsubstituted hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, a carboxy group, or an amino group. And a hydrocarbon group having 1 to 6 carbon atoms substituted with a group.
  • examples of the compound represented by the formula (A) include 1-thioglycerol, L-cysteine, thiomalic acid and the like.
  • the hydrocarbon groups and substituents represented by R 1B to R 4B have the same meanings as the hydrocarbons and substituents represented by R 1A to R 5A in the formula (A) described above.
  • the substituted or unsubstituted hydrocarbon group represented by R 1B to R 4B include hydrocarbon groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a t-butyl group. It is done.
  • Examples of the compound represented by the formula (B) include catechol and t-butylcatechol.
  • R 1C hydrocarbon groups and substituents represented by R 2C and R N, respectively and hydrocarbon and substituents represented by R 1A ⁇ R 5A of formula (A) described above synonymous is there.
  • R 1C, as a substituted or unsubstituted hydrocarbon group represented by R 2C and R N are, for example, include a methyl group, an ethyl group, a propyl group and a hydrocarbon group having 1 to 6 carbon atoms such as butyl group, It is done.
  • R 1C and R 2C may be combined to form a ring, and examples thereof include a benzene ring.
  • R 1C and R 2C are combined to form a ring, it may further have a substituent (for example, a hydrocarbon group having 1 to 5 carbon atoms).
  • substituent for example, a hydrocarbon group having 1 to 5 carbon atoms.
  • Examples of the compound represented by the formula (C) include 1H-1,2,3-triazole, benzotriazole, and 5-methyl-1H-benzotriazole.
  • substituted or unsubstituted tetrazole examples include an unsubstituted tetrazole, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted amino group as a substituent (the substituent includes an alkyl group having 1 to 6 carbon atoms).
  • the substituent includes an alkyl group having 1 to 6 carbon atoms.
  • tetrazole having an alkyl group having 1 to 3 carbon atoms is more preferable.
  • silicon compounds can be suitably used as corrosion inhibitors, and include tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, or diphenyl. Dimethoxysilane is preferred. Of these, methyltrimethoxysilane is more preferable.
  • the content thereof is preferably 0.01 to 5% by mass, more preferably 0.05 to 5% by mass with respect to the total mass of the treatment liquid, and 0 More preferably, the content is 1 to 3% by mass.
  • Corrosion inhibitors may be used alone or in appropriate combination of two or more. When using in combination of 2 or more types, the total content should just be in the above-mentioned range.
  • the treatment liquid of the present invention preferably contains an amine compound. It does not specifically limit as an amine compound, A hydroxylamine, a hydroxylamine salt, an alkanolamine, etc. are mentioned. Especially, it is preferable that it is at least 1 sort (s) chosen from a hydroxylamine and a hydroxylamine salt from a viewpoint of accelerating
  • hydroxylamine according to hydroxylamine and hydroxylamine salt refers to hydroxylamines in a broad sense including substituted or unsubstituted alkylhydroxylamine, and the effects of the present application are obtained in any case. be able to.
  • the hydroxylamine is not particularly limited, and preferred embodiments include unsubstituted hydroxylamine and hydroxylamine derivatives.
  • the hydroxylamine derivative is not particularly limited, and examples thereof include O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N, N-dimethylhydroxylamine, N, O-dimethylhydroxylamine, N-ethyl.
  • the salt of hydroxylamine is preferably the inorganic acid salt or organic acid salt of hydroxylamine described above, and is a salt of an inorganic acid formed by bonding a nonmetal such as Cl, S, N, and P with hydrogen. More preferred is a salt of any one of hydrochloric acid, sulfuric acid, and nitric acid.
  • Hydroxylamine salts used to form the processing solution of the present invention include hydroxylammonium nitrate (also referred to as HAN), hydroxylammonium sulfate (also referred to as HAS), and hydroxylamine hydrochloride (also referred to as HAC).
  • HAS hydroxylammonium sulfate
  • HAC hydroxylamine hydrochloride
  • hydroxylammonium phosphate hydroxylammonium hydrochloride
  • N, N-diethylhydroxylammonium sulfate N, N-diethylhydroxylammonium nitrate
  • an organic acid salt of hydroxylamine can be used, and examples thereof include hydroxylammonium citrate, hydroxylammonium oxalate, and hydroxylammonium fluoride.
  • hydroxylamine or its salt may be sufficient as the processing liquid of this invention.
  • hydroxylamine or hydroxylammonium sulfate is preferable and hydroxylammonium sulfate is more preferable from the viewpoint that the desired effect of the present application can be remarkably obtained.
  • the content is 0.1 to 15 with respect to the total mass of the treatment liquid from the viewpoint of further improving the effect of the present invention. It is preferably in the range of mass%, more preferably in the range of 0.5 to 10 mass%.
  • alkanolamine as an amine compound from the viewpoint of corrosion prevention while promoting solubilization of the additive component and the organic film and residue on the substrate.
  • the alkanolamine may be any of primary amine, secondary amine, and tertiary amine, and is preferably monoamine, diamine, or triamine, and more preferably monoamine.
  • the alkanol group of the amine preferably has 1 to 5 carbon atoms.
  • a compound represented by the following formula (2) is preferable.
  • R 1 R 2 —N—CH 2 CH 2 —O—R 3 (In Formula (2), R 1 and R 2 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyethyl group, and R 3 each independently represents a hydrogen atom or a hydroxyethyl group.
  • alkanolamine examples include monoethanolamine, diethanolamine, triethanolamine, tert-butyldiethanolamine, isopropanolamine, 2-amino-1-propanol, 3-amino-1-propanol, isobutanolamine, 2- Examples include amino-2-ethoxy-propanol and 2-amino-2-ethoxy-ethanol, also known as diglycolamine.
  • Alkanolamines may be used alone or in combination of two or more.
  • the content thereof is preferably 0.1 to 60% by mass, more preferably 0.5 to 50% by mass with respect to the total mass of the treatment liquid. More preferably, it is 5 to 20% by mass.
  • the treatment liquid of the present invention may contain an oxidizing agent.
  • the oxidizing agent may be a compound having an oxidizing action.
  • hydrogen peroxide, ammonium persulfate, chloric acid, chlorous acid, hypochlorous acid, perchloric acid, permanganic acid are more excellent in terms of both the ability to remove residues and the corrosiveness to insulating films.
  • At least one compound selected from the group consisting of iodic acid, hypoiodic acid, periodic acid, and orthoperiodic acid is preferred.
  • hydrogen peroxide or orthoperiodic acid is particularly preferable.
  • the oxidizing agents may be used alone or in combination of two or more.
  • the content thereof is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass with respect to the total mass of the treatment liquid.
  • the treatment liquid of the present invention may contain a halide.
  • the halide promotes decomposition and solubilization of the residue.
  • the halide is a compound containing one or more halogen elements, and examples of the halogen element include one or more selected from the group consisting of fluorine, chlorine, bromine, and iodine.
  • fluoride or chloride is preferable from the viewpoint of promoting decomposition and solubilization of the residue, and fluoride is particularly preferable from the viewpoint of excellent effects.
  • the fluoride is not particularly limited, but hydrofluoric acid (HF), fluorosilicic acid (H 2 SiF 6 ), fluoroboric acid, fluorosilicate ammonium salt ((NH 4 ) 2 SiF 6 ), hexafluorophosphoric acid Tetramethylammonium, ammonium fluoride, ammonium fluoride salt, ammonium bifluoride salt, tetrafluoroboric acid quaternary ammonium represented by formula NR 4 BF 4 , tetrafluoroboric acid quaternary represented by PR 4 BF 4 Quaternary phosphonium and tetrabutylammonium tetrafluoroborate (TBA-BF 4 ) can be mentioned.
  • hydrofluoric acid HF
  • fluorosilicic acid H 2 SiF 6
  • fluoroboric acid fluorosilicate ammonium salt
  • (NH 4 ) 2 SiF 6 ) fluorosilicate ammonium salt
  • R may be hydrogen, a linear, branched, or cyclic C1-C6 alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group), and a linear or branched C6 -C10 aryl group (for example, benzyl group).
  • Examples of the quaternary ammonium tetrafluoroborate represented by the formula NR 4 BF 4 and the quaternary phosphonium tetrafluoroborate represented by PR 4 BF 4 include, for example, tetramethylammonium tetrafluoroborate, tetrafluorobora Examples include tetraethylammonium acid, tetrapropylammonium tetrafluoroborate, and tetrabutylammonium tetrafluoroborate.
  • Fluoride may be used alone or in combination of two or more. Among these, ammonium fluoride or fluorosilicic acid is preferable in that the desired effect of the present application can be remarkably obtained.
  • the content thereof is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass, and preferably 0.1 to 15% by mass with respect to the total mass of the treatment liquid. More preferably, it is 1 to 5% by mass.
  • the treatment liquid may further contain a chelating agent.
  • the chelating agent chelates with the oxidized metal contained in the residue. For this reason, the recyclability of a processing liquid improves by adding a chelating agent.
  • it does not specifically limit as a chelating agent, It is preferable that it is polyamino polycarboxylic acid.
  • the polyaminopolycarboxylic acid is a compound having a plurality of amino groups and a plurality of carboxylic acid groups.
  • polyaminopolycarboxylic acid examples include mono- or polyalkylene polyamine polycarboxylic acid, polyaminoalkane polycarboxylic acid, polyaminoalkanol polycarboxylic acid, and hydroxyalkyl ether polyamine polycarboxylic acid.
  • polyaminopolycarboxylic acid examples include butylene diamine tetraacetic acid, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N, N, N ′, N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,6-hexamethylene-diamine-N, N , N ′, N′-tetraacetic acid, N, N-bis (2-hydroxybenzyl) ethylenediamine-N, N-diacetic acid, diaminopropanetetraacetic acid, 1,4,7,10-tetraaza
  • DTPA diethylenetriaminepentaacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • trans-1,2-diaminocyclohexanetetraacetic acid is preferred.
  • DTPA diethylenetriaminepentaacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • trans-1,2-diaminocyclohexanetetraacetic acid is preferred.
  • the content thereof is preferably 0.01 to 5% by mass, and more preferably 0.01 to 3% by mass with respect to the total mass of the treatment liquid.
  • the pH of the treatment liquid of the present invention is not particularly limited, but when it contains hydroxylamine and a hydroxylamine salt as optional components, it is preferably at least pKa of the conjugate acid of hydroxylamine and hydroxylamine salt.
  • pKa or more of the conjugate acid of hydroxylamine and hydroxylamine salt residue removability is dramatically improved.
  • the residue removal property is more excellent.
  • the pKa of hydroxylamine conjugate acid is about 6.
  • the pH of the treatment liquid of the present invention is preferably pH 7.0 as a lower limit, more preferably pH 7.5, and particularly preferably pH 8.0.
  • the upper limit is preferably pH 14, and more preferably pH 13.4.
  • pH adjusting agent known ones can be used, but generally it is preferable that no metal ion is contained.
  • ammonium hydroxide, monoamines, imines for example, 1,8-diazabicyclo [5.4 0.0] undecan-7-ene, and 1,5-diazabicyclo [4.3.0] non-5-ene
  • imines for example, 1,8-diazabicyclo [5.4 0.0] undecan-7-ene, and 1,5-diazabicyclo [4.3.0] non-5-ene
  • 1,4-diazabicyclo [2.2.2] octane 1,4-diazabicyclo [2.2.2] octane
  • guanidine salts eg, carbonic acid Any of these can be used to obtain the effects of the present invention.
  • ammonium hydroxide or imines for example, 1,8-diazabicyclo [5.4.0] undecan-7-ene and 1,5-diazabicyclo [4.3.0] non-5-ene
  • the pH adjusters may be used alone or in appropriate combination of two or more.
  • the content of the pH adjusting agent in the treatment liquid is not particularly limited as long as the treatment liquid can achieve a desired pH, but generally 0.1 to The content is preferably 5% by mass, more preferably 0.1 to 2% by mass.
  • the treatment liquid of the present invention may contain other additives as long as the effects of the present invention are achieved.
  • additives include surfactants, antifoaming agents, rust preventives, and preservatives described later.
  • the treatment liquid of the present invention may be a kit obtained by dividing the raw material into a plurality of parts.
  • a kit is preferable.
  • a liquid composition containing at least one hydroxylamine compound selected from hydroxylamine and a hydroxylamine salt in water as the first liquid is used.
  • the aspect which prepares and prepares the liquid composition containing another component as a 2nd liquid is mentioned.
  • a hydrophilic organic solvent, an inorganic anion, and a quaternary ammonium salt may be contained in any of them.
  • a liquid composition containing a quaternary ammonium salt is prepared as the first liquid
  • a liquid composition containing an oxidizing agent is prepared as the second liquid.
  • a mode in which both solutions are mixed to prepare a treatment solution and then applied to the above treatment in a timely manner is preferable.
  • Other components such as a hydrophilic organic solvent and inorganic anion may be contained in either. By doing in this way, it does not cause deterioration of the liquid performance by decomposition
  • Content of each component in a 1st liquid and a 2nd liquid can be suitably set as content after mixing based on content described previously.
  • the treatment liquid of the present invention can be stored, transported and used in any container as long as corrosivity does not matter (whether or not it is a kit).
  • a container a container having a high cleanliness and a small amount of impurity elution is preferable for semiconductor applications.
  • the containers that can be used include, but are not limited to, “Clean Bottle” series manufactured by Aicero Chemical Co., Ltd., “Pure Bottle” manufactured by Kodama Resin Co., Ltd., and the like.
  • the inner wall of the container is made of a resin different from at least one resin selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a metal that has been subjected to rust prevention and metal elution prevention treatment. Preferably it is formed.
  • a fluororesin perfluoro resin
  • elution of ethylene and propylene oligomers is achieved compared to the case where a container whose inner wall is made of polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin. The occurrence of defects can be suppressed.
  • a FluoroPure PFA composite drum manufactured by Entegris may be mentioned.
  • a FluoroPure PFA composite drum manufactured by Entegris may be mentioned.
  • it is described in, for example, page 4 of Japanese Patent Publication No. 3-502677, page 3 of International Publication No. 2004/016526, pages 9 and 16 of International Publication No. 99/46309, etc.
  • Containers can also be used.
  • the treatment liquid of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects.
  • the material of the filter can be used without particular limitation as long as it has been conventionally used for filtration.
  • a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, and a polyolefin resin (including high density and ultrahigh molecular weight) such as polyethylene and polypropylene (PP) can be used.
  • a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, and a polyolefin resin (including high density and ultrahigh molecular weight) such as polyethylene and polypropylene (PP)
  • PP polypropylene
  • nylon is preferable.
  • the pore size of the filter is suitably about 0.001 to 1.0 ⁇ m, preferably about 0.02 to 0.5 ⁇ m, more preferably about 0.01 to 0.1 ⁇ m. By setting it as this range, it becomes possible to remove fine foreign matters, such as impurities or aggregates contained in the processing liquid, while suppressing filtration clogging.
  • filters different filters may be combined. In that case, filtering with each filter may be performed only once or may be performed twice or more. This filtering twice or more means, for example, a case where the liquid is circulated and filtering is performed twice or more by the same filter.
  • the filtering can be performed by combining different filters as described above.
  • the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering.
  • the pore diameter here can refer to the nominal value of the filter manufacturer.
  • the second filter can be a filter formed of the same material as the first filter described above.
  • the pore size of the second filter is suitably about 0.01 to 1.0 ⁇ m, preferably about 0.1 to 0.5 ⁇ m. By setting it as this range, when the component particles are contained in the liquid, the foreign matters mixed in the liquid can be removed while the component particles remain. For example, only a part of the components of the treatment liquid to be finally prepared is mixed in advance to prepare a mixed liquid, and the mixed liquid is filtered by the first filter, and then the first filter is used. The remaining components for constituting the treatment liquid may be added to the mixed liquid after filtering, and the second filtering may be performed on the mixed liquid.
  • the treatment liquid of the present invention has an ion concentration of metal (Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni, Fe, Co, and Zn metal elements) contained as impurities in the liquid. Is preferably 5 ppm or less (preferably 1 ppm or less). In particular, in the manufacture of the most advanced semiconductor elements, it is assumed that a higher-purity processing solution is required, so that the metal concentration is lower than the ppm order, that is, ppb order or less. More preferably, it is more preferably in the order of ppt (all the above concentrations are based on mass), and it is particularly preferable that the concentration is not substantially contained.
  • metal Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni, Fe, Co, and Zn metal elements
  • distillation and / or an ion exchange resin is used in at least one of a raw material stage used in manufacturing a processing liquid and a stage after preparing the processing liquid. Sufficient filtration.
  • the elution of impurities as shown in the section describing the container that contains the treatment liquid may occur. It is mentioned to use few containers.
  • the treatment liquid of the present invention preferably has few impurities, such as a metal content, in the liquid.
  • the Na, K, and Ca ion concentrations in the liquid are more preferably in the range of 5 ppm or less (mass basis).
  • the treatment liquid does not substantially contain coarse particles.
  • the coarse particles contained in the treatment liquid are particles such as dust, dust, organic solids, and inorganic solids contained as impurities in the raw material, and dust and dust brought in as contaminants during the preparation of the treatment liquid. These include particles such as organic solids and inorganic solids, which finally exist as particles without being dissolved in the treatment liquid.
  • the amount of coarse particles present in the treatment liquid can be measured in a liquid phase using a commercially available measuring apparatus in a light scattering type in-liquid particle measurement method using a laser as a light source.
  • the processing application and the object to be processed using the processing liquid of the present invention are not particularly limited, but the organic film on the substrate (for example, various resists used as a mask at the time of etching, a permanent film, etc.) is removed or removed. It can be preferably used for cleaning and removing dry etching residue or dry ash residue adhering thereto. That is, the treatment liquid of the present invention can be suitably applied to a stripping liquid, a cleaning liquid, a rinsing liquid, and the like.
  • the substrate in the object to be processed is not particularly limited, and examples include a silicon substrate (Si substrate), a silicon oxide substrate (SiO substrate), and a silicon nitride substrate (SiN substrate). Further, the substrate may include not only the wafer but also the entire substrate structure having a circuit structure applied thereto.
  • the treatment liquid of the present invention is preferably applied to a substrate provided with a circuit structure because corrosiveness to a metal material (for example, electrode material) such as an electrode or wiring disposed on the substrate is suppressed. it can.
  • the permanent film removal method using the treatment liquid of the present invention can include a step of applying the treatment liquid to the substrate on which the permanent film is provided. As a result, the treatment liquid described above penetrates into the permanent film and the interface between the permanent film and the substrate, and the permanent film can be peeled and removed.
  • the method for applying the treatment liquid in the permanent film removal method is not particularly limited. There is a method in which the treatment liquid and the permanent film or the substrate are brought into contact with each other by ejection from the ejection port of the ejection mechanism or ejection (spraying) from the ejection port of the ejection mechanism.
  • the processing liquid introduced into the introduction port of the apparatus reaches the discharge port via a flow path connected to the introduction port, and is discharged from the discharge port to be processed into a processing container (for example, a processing vessel). It adheres to the substrate placed in the tank.
  • the flow path may have a path for reusing the processing liquid.
  • the substrate may be placed on a rotary table having a rotation driving unit, and may be rotated together with the rotary table when or after the treatment liquid is attached.
  • the single wafer apparatus has a treatment tank. In the processing tank, processing such as transport and rotation of the substrate, supply of the processing liquid, and the like are performed. Thereby, it is preferable that the substrate is brought into contact with the treatment liquid in the treatment tank and the treatment liquid is applied to the substrate (e.g., ejection, jetting, flowing down, and dropping).
  • Advantages of using the above-mentioned single-wafer type apparatus include good reproducibility because a fresh processing liquid is always supplied, and high in-plane uniform processing performance.
  • the single wafer apparatus preferably includes a nozzle in its treatment tank.
  • a method of applying the processing liquid to the substrate there is a method of discharging the processing liquid while swinging the nozzle in the surface direction of the substrate and applying the processing liquid to the substrate. Use of this method is preferable in that deterioration of the treatment liquid can be prevented.
  • the treatment temperature in the permanent film removing method is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and further preferably 60 ° C. or higher. As an upper limit, it is preferable that it is 100 degrees C or less, and it is more preferable that it is 90 degrees C or less.
  • the processing temperature is measured under the following conditions in a single wafer type apparatus.
  • a radiation thermometer IT-550F (trade name) manufactured by HORIBA, Ltd. is fixed to a height of 30 cm above the wafer in the single wafer type apparatus.
  • a thermometer is directed onto the wafer surface 2 cm outside from the center of the wafer, and the temperature is measured while flowing the processing liquid. The temperature is digitally output from the radiation thermometer and recorded continuously by a personal computer.
  • a value obtained by averaging temperatures for 10 seconds at which the temperature is stabilized is defined as a temperature on the wafer.
  • the temperature in the tank can be held and set until it stabilizes for a predetermined time (for example, 1 minute).
  • a predetermined time for example, 1 minute.
  • the temperature may be maintained and set until the temperature in the circulation channel is stabilized for a predetermined time (for example, 1 minute).
  • the supply rate of the treatment liquid when using a single wafer apparatus is not particularly limited, but is preferably 0.05 to 5 L / min, and more preferably 0.1 to 3 L / min. By setting it as said range, it is preferable at the point which can ensure the stable performance at the time of continuous processing, ensuring the uniformity in the surface of a process target more favorably.
  • the substrate is rotated, although it depends on the size and the like, it is preferable to rotate the substrate at 50 to 1000 rpm from the same viewpoint as described above.
  • the moving speed at the time of moving a discharge outlet (nozzle) is not specifically limited, It is preferable that it is 0.1 cm / s or more, and it is more preferable that it is 1 cm / s or more.
  • the upper limit is preferably 30 cm / s or less, and more preferably 15 cm / s or less.
  • the movement trajectory line may be a straight line or a curved line (for example, an arc shape). In any case, the moving speed can be calculated from the actual distance of the trajectory line and the time spent for the movement.
  • the time required for processing one substrate is preferably in the range of 10 to 1200 seconds.
  • an immersion method dip treatment
  • a substrate provided with a permanent film is immersed in a treatment liquid in a treatment tank, and the substrate and the treatment liquid are brought into contact in the treatment tank.
  • substrate it is as having shown with the process temperature in the permanent film removal method mentioned above.
  • other conditions for example, time for immersing the substrate
  • the permanent film examples include a finely processed color filter, a transparent insulating film, and a resin lens, which are applied to manufacture of a solid-state imaging device and an image display device. These materials are not particularly limited, and known materials can be used.
  • the above-described permanent film removal method can be applied after the manufacture of the semiconductor substrate product. That is, for example, when a permanent film already formed on a semiconductor substrate product has a defect or the like, the permanent film can be removed from the semiconductor substrate product and the substrate can be reused.
  • the semiconductor substrate product is a general term for products including semiconductor elements obtained through a process such as a lithography process using the substrate.
  • Such a permanent film unlike a resist that is removed after an etching process in the manufacture of a semiconductor substrate product, remains undissolved even by development, and is not assumed to be removed after processing. Expected to be difficult. However, the permanent film can be removed satisfactorily by using the treatment liquid of the present invention.
  • treatment liquid of the present invention can be suitably used for removing color filters described in, for example, WO2015 / 115539 publication and JP2015-31800A.
  • the treatment liquid of the present invention can be applied not only to the removal of the permanent film formed on the substrate, but also as a stripping removal liquid for various resists used as a mask during etching in the manufacture of semiconductor substrate products. . That is, the resist can be used as a stripping removal liquid for removing the resist dissolved by processing such as development and the residue. The removal and removal of the various resists can be performed in the same manner as the permanent film.
  • the material of the photoresist is not particularly limited, and a known material can be used.
  • the composition is not particularly limited, water and, A hydrophilic organic solvent, A quaternary ammonium salt, 0.001 mass ppt to 1 mass ppm of inorganic anions with respect to the total mass of the treatment liquid, Further, at least one embodiment selected from the following (1) to (3) is preferable.
  • the treatment liquid further contains at least one selected from a corrosion inhibitor and an amine compound.
  • a corrosion inhibitor and an amine compound.
  • an aprotic polar solvent or a sulfone solvent is included.
  • the treatment liquid further contains a surfactant.
  • the treatment liquid of the present invention When the treatment liquid of the present invention is applied to the removal of a permanent film and an organic film such as a resist, the treatment liquid may be an aqueous treatment liquid or an organic solvent treatment liquid.
  • the permanent film is an organic compound film, an organic solvent-based treatment liquid is preferable.
  • aprotic polar organic solvents include dimethyl sulfoxide (hereinafter abbreviated as DMSO), sulfolane, dimethyl sulfone, N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl.
  • NMP N-vinyl-2-pyrrolidone
  • ⁇ -caprolactam 1,3-dimethyl-2-imidazolidinone
  • tetramethylurea hexamethylphosphate triamide
  • ⁇ -butyrolactone ⁇ -Valerolactone
  • ⁇ -caprolactone acetonitrile
  • pyridine dimethoxyethane
  • diglyme triglyme
  • ethylene carbonate propylene carbonate and the like.
  • DMSO and NMP are preferable and DMSO is more preferable in terms of peelability and permeability.
  • the removal property of the resist formed in contact with the hydrophobic resist and the hydrophobic material is further improved, and damage to the electrode can be further suppressed.
  • aprotic polar organic solvents may be used alone or in combination of two or more.
  • nonionic, anionic, cationic surfactants, and amphoteric surfactants can be used as the surfactant.
  • the content of the surfactant is preferably 0.0001 to 5% by mass, more preferably 0.0001 to 1% by mass.
  • Nonionic surfactants include, for example, polyalkylene oxide alkylphenyl ether surfactants, polyalkylene oxide alkyl ether surfactants, block polymer surfactants composed of polyethylene oxide and polypropylene oxide, and polyoxyalkylene distyrene. Phenyl ether surfactants, polyalkylene tribenzylphenyl ether surfactants, and acetylene polyalkylene oxide surfactants.
  • Anionic surfactants include alkyl sulfates, alkyl sulfonic acids, alkyl benzene sulfonic acids, alkyl naphthalene sulfonic acids, alkyl diphenyl ether sulfonic acids, polyoxyethylene alkyl ether carboxylic acids, polyoxyethylene alkyl ether acetic acids, polyoxyethylene alkyl ethers.
  • Examples include propionic acid and salts thereof.
  • Examples of the cationic surfactant include quaternary ammonium salt surfactants and alkyl pyridium surfactants.
  • amphoteric surfactants include betaine surfactants, amino acid surfactants, imidazoline surfactants, and amine oxide surfactants.
  • the substrate described above can be used as the substrate on which the resist is disposed.
  • the resist film to be processed is not particularly limited, and examples thereof include positive type, negative type, and positive / negative type photoresists.
  • positive resists include (meth) acrylate resin-based, vinyl cinnamate-based, cyclized polyisobutylene-based, azo-novolak resin-based, and diazoketone-novolak resin-based, as well as novolac-based resins and polyhydroxystyrene-based resins.
  • the resin include at least one resin.
  • the negative resist examples include an azide-cyclized polyisoprene system, an azide-phenol resin system, and a chloromethyl polystyrene system.
  • specific examples of the positive / negative resist include poly (p-butoxycarbonyloxystyrene) type.
  • Other examples of resists for patterning are disclosed in Japanese Patent Nos. 5222804, 5244740, 5244933, 5286236, 5210755, 5277128, 5303604, 5216892, 5553139, 5531578, and 5155803. Can be referred to and are incorporated herein by reference.
  • the permanent film to be treated is not particularly limited, and examples thereof include a color filter resist (hereinafter also referred to as “color resist”).
  • color resist a color resist to which the treatment liquid of the present invention can be preferably applied will be described in detail.
  • the color filter has a component such as a coloring material that is not included in a normal resist, and it is expected that it is difficult to remove it.
  • the treatment liquid of the present invention exhibits its effect well in removing the color filter. Therefore, the treatment liquid of the present invention is particularly suitable for removing color filters among permanent films.
  • RGB 5000 series / 6000 series (trade name) and CMY 3000 series (trade name) manufactured by FUJIFILM Corporation can be suitably used as the color resist.
  • the color filter forming material and the forming method will be described in detail with an example.
  • Each pixel of the color filter can be formed by curing the following colored curable resin composition.
  • the colored curable resin composition include an alkali-soluble resin, a polymerizable compound, a polymerization initiator, and a colorant.
  • alkali-soluble resin what has at least 1 group which promotes alkali solubility in a molecule
  • numerator is preferable.
  • polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, or acrylic / acrylamide copolymer resins are preferred.
  • an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin is preferable.
  • Examples of the group that promotes alkali solubility include a carboxy group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Those which are soluble in a solvent and can be developed with a weak alkaline aqueous solution are preferred, and (meth) acrylic acid is particularly preferred. These acidic groups may be only one type or two or more types.
  • the alkali-soluble resin is preferably a polymer having a carboxy group in the main chain or side chain.
  • methacrylic acid copolymer such as methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, and novolak type resin
  • alkali-soluble phenol resins acidic cellulose derivatives having a carboxylic acid in the side chain, and those obtained by adding an acid anhydride to a polymer having a hydroxyl group.
  • a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable.
  • Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds.
  • Examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (iso) pentyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) ) Acrylate, naphthyl (meth) acrylate,
  • Examples of the vinyl compound include styrene, ⁇ -methyl styrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like.
  • Examples of N-substituted maleimide monomers described in JP-A-10-300922 include N-phenylmaleimide and N-cyclohexylmaleimide.
  • the alkali-soluble resin preferably has a polymerizable group.
  • Examples of the polymerizable group include an ethylenically unsaturated bond group. Specifically, a (meth) acryloyl group or a vinyl group is preferable, and a (meth) acryloyl group is more preferable.
  • the acrylic polymer is preferably a vinyl polymer having a repeating unit derived from one or more of (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylamide.
  • the synthesis of the polymerizable alkali-soluble resin can be performed based on the synthesis method described in paragraph Nos. 0027 to 0057 of JP-A No. 2003-262958. Of these, the synthesis method 1 in the publication is preferred. As the exemplified compounds, the compounds described in paragraph Nos. 0058 to 0061 of the above-mentioned JP-A No. 2003-262958 can be referred to and incorporated in the present specification. Specific examples of the compound include the following compound (resin P-1) (weight average molecular weight: 14000).
  • the alkali-soluble resin is also preferably a polymer represented by the following formula.
  • L X1 represents a single bond or a linking group.
  • the linking group include the linking group L described above. Of these, a single bond is preferable.
  • R X1 and R Y1 are a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a cyano group, preferably a hydrogen atom or a methyl group.
  • R A is an acidic group. The preferable thing is synonymous with the above.
  • R Y2 represents a substituent, and among them, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an aryl group (having 6 to 22 carbon atoms) Preferably 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms), an aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 15 carbon atoms, and particularly preferably 7 to 11 carbon atoms). Is preferred. These groups may further have a substituent, and examples of the further substituent include a hydroxyl group and a carboxy group.
  • nx and ny are mole fractions, and nx + ny may be less than 1 (meaning that it may have other repeating units), and is preferably 1.
  • nx is preferably 0.05 or more, more preferably 0.1 or more, and still more preferably 0.2 or more.
  • 0.7 or less is preferable, 0.6 or less is more preferable, and 0.5 or less is still more preferable.
  • the lower limit of ny is preferably 0.3 or more, more preferably 0.4 or more, and still more preferably 0.6 or more.
  • 0.9 or less is preferable and 0.8 or less is more preferable.
  • the alkali-soluble resin is preferably soluble in a tetramethylammonium hydroxide (TMAH) aqueous solution having a concentration of 0.1% by mass or more at 23 ° C. Furthermore, it is preferable that it is soluble in 1% by mass or more of TMAH aqueous solution, and further soluble in 2% by mass or more of TMAH aqueous solution.
  • TMAH tetramethylammonium hydroxide
  • the acid value of the alkali-soluble resin is preferably 30 to 200 mgKOH / g, more preferably 70 to 120 mgKOH / g. By setting it as such a range, the image development residue of an unexposed part can be reduced effectively.
  • the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2000 to 50000, particularly preferably 7000 to 20000.
  • the content of the alkali-soluble resin is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, and particularly preferably 20 to 35% by mass with respect to the total solid content of the colored curable resin composition. It is.
  • Alkali-soluble resin may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the polymerizable compound may be a compound having a polymerizable group in the molecule, and among them, a monomer having an ethylenically unsaturated double bond (hereinafter sometimes referred to as “specific monomer”) is preferable. .
  • the specific monomer is preferably a polyfunctional monomer.
  • a specific monomer may be used individually by 1 type, and may use 2 or more types together.
  • the specific monomer is preferably a (meth) acrylate monomer.
  • the specific monomer is preferably further represented by the following formulas (MO-1) to (MO-6).
  • n 0 to 14, respectively, and m is 1 to 8, respectively.
  • a plurality of R, T and Z present in one molecule may be the same or different.
  • T is an oxyalkylene group
  • the terminal on the carbon atom side is bonded to R.
  • At least one of R is a polymerizable group.
  • n is preferably from 0 to 5, and more preferably from 1 to 3.
  • m is preferably 1 to 5, and more preferably 1 to 3.
  • dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available product: KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product: KAYARAD DPHA; Nippon Kayaku Co., Ltd.)
  • diglycerin EO ethylene oxide
  • meth) acrylate commercially available product is M-460; Toa Gosei)
  • the molecular weight of the polymerizable compound is not particularly limited, but is preferably 300 or more and 1500 or less, and more preferably 400 or more and 700 or less.
  • the content of the polymerizable compound with respect to the total solid content in the composition is preferably in the range of 1 to 50% by mass, more preferably in the range of 3 to 40% by mass, and 5 to 30% by mass. More preferably, it is in the range of%. Within this range, the curability is good and preferable without excessively reducing the refractive index and transparency.
  • a polymeric compound may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the polymerization initiator may be either a thermal polymerization initiator or a photopolymerization initiator, but a photopolymerization initiator is preferred.
  • an oxime compound among the above.
  • commercially available products such as IRGACURE OXE01 (lower formula) or IRGACURE OXE02 (lower formula) can be suitably used.
  • the polymerization initiator is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 0.5 to 10% by mass, and particularly preferably 1 to 8% by mass in the solid content of the colored curable resin composition. It is a range. You may use a polymerization initiator in combination of 2 or more type as needed.
  • Colorant is not particularly limited, and various dyes and pigments can be used.
  • chromatic colorants such as red, magenta, yellow, blue, cyan, and green that form color pixels of color filters, and black that is commonly used for black matrix formation Any of the above colorants (black colorants) can be used.
  • the colorant is preferably at least one selected from red, magenta, yellow, blue, cyan, and green.
  • the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like.
  • iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony examples thereof include metal oxides such as silver and complex oxides of the above metals. Titanium nitrides, silver tin compounds, silver compounds, and the like can also be used.
  • Organic pigments include perylene pigment, perinone pigment, quinacridone pigment, quinacridone quinone pigment, anthraquinone pigment, anthanthrone pigment, benzimidazolone pigment, disazo pigment, azo pigment, indanthrone pigment, phthalocyanine pigment, triarylcarbonium pigment, dioxazine
  • Examples include pigments, aminoanthraquinone pigments, diketopyrrolopyrrole pigments, indigo pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, pyranthrone pigments, and isoviolanthrone pigments.
  • the dye examples include triarylmethane, pyrazoleazo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazoleazo, pyridoneazo, cyanine, phenothiazine Azomethine, pyrrolopyrazole, azomethine, xanthene, phthalocyanine, benzopyran, indigo, and pyromethene dyes can be used. Moreover, you may use the multimer of these dyes.
  • the average primary particle size is preferably 5 nm or more, particularly preferably 30 nm or more.
  • 1 micrometer or less is preferable, 500 nm or less is more preferable, and 100 nm or less is especially preferable.
  • the particle size is measured using a dynamic light scattering particle size distribution analyzer (Nanotrack Nano-Wave-EX150 [trade name] manufactured by Nikkiso, LB-500 [trade name] manufactured by HORIBA, Ltd.). Do it. The procedure is as follows. The sample dispersion is dispensed into a 20 ml sample bottle and diluted with an insoluble solvent (eg water) to a solid component concentration of 0.2% by weight.
  • an insoluble solvent eg water
  • the content of the colorant is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more in the solid content of the colored curable resin composition.
  • limiting in particular about an upper limit Preferably it is 80 mass% or less, More preferably, it is 60 mass% or less. According to the treatment liquid of the present invention, the color resist can be sufficiently removed even when the colorant is contained in a large amount as described above.
  • a coloring curable resin composition may contain a dispersing agent.
  • a dispersant for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type) Copolymer, naphthalenesulfonic acid formalin condensate), polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment dispersant and the like.
  • a polymer dispersant for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type) Copolymer, naphthalenesulfonic acid formalin condensate
  • polyoxyethylene alkyl phosphate ester polyoxyethylene alkyl amine
  • the polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to its structure.
  • Specific examples of the pigment dispersant include “Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161, 162 manufactured by BYK Chemie.
  • the concentration of the dispersant is preferably 1 to 100 parts by weight, more preferably 3 to 100 parts by weight, and still more preferably 5 to 80 parts by weight with respect to 1 part by weight of the colorant. Further, the content is preferably 5 to 30% by mass with respect to the total solid content of the colored curable resin composition.
  • a dispersing agent may be used independently and may be used in combination of 2 or more type.
  • surfactant You may add various surfactant to a colored curable resin composition from a viewpoint of improving applicability
  • various surfactants such as a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.
  • the content is preferably in the range of 1 to 40% by mass and more preferably 5 to 20% by mass with respect to the total mass of the solid content of the colored curable resin composition.
  • the colored curable resin composition may contain other components as appropriate.
  • other components include organic solvents, ultraviolet absorbers, adhesion improvers, sensitizing dyes, co-sensitizers, diluents, plasticizers, and sensitizers.
  • Preparation of the colored curable resin composition and formation of the cured film may be performed by a general method, but in the following, formation of a color filter using the colored curable resin composition is an example. Further details are given in As a support for forming the color filter, for example, an imaging element (light receiving element) such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate).
  • a substrate for example, a silicon substrate.
  • the above-described substrate such as a solid-state imaging device substrate can be used.
  • the coloring pattern may be formed on the imaging element forming surface side (front surface) of the solid-state imaging element substrate, or may be formed on the imaging element non-forming surface side (back surface).
  • a light-shielding film may be provided between the image sensors in the solid-state image sensor substrate and on the back surface of the solid-state image sensor substrate.
  • an undercoat layer may be partially provided on the support in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.
  • Color filters on the hydrophilic layer and the color filter on the hydrophobic layer coexist on one substrate by forming color filters on both the areas with and without the primer layer. Can be made.
  • an overcoat layer described later can be used for the undercoat layer.
  • various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied.
  • the colored curable resin composition layer coated on the support can be dried (pre-baked) at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, an oven, or the like.
  • the colored curable resin composition layer formed in the colored curable resin composition layer forming step is subjected to pattern exposure through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper, for example.
  • an exposure apparatus such as a stepper
  • radiation light
  • ultraviolet rays such as g-line and i-line are particularly preferable (particularly preferably i-line).
  • Irradiation dose is preferably 30 ⁇ 1500mJ / cm 2, more preferably 50 ⁇ 1000mJ / cm 2, more preferably 80 ⁇ 500mJ / cm 2.
  • the colored curable resin composition of the light non-irradiated portion in the exposure step is eluted into the alkaline aqueous solution, and only the photocured portion remains.
  • the developer an organic alkali developer that does not easily cause damage to the underlying image sensor and circuit is desirable.
  • the development temperature is usually 20 ° C. to 30 ° C., and the development time is, for example, 20 seconds to 90 seconds. In order to remove the residue more, in recent years, it may be carried out for 120 seconds to 180 seconds. Furthermore, in order to further improve residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.
  • Examples of methods and materials for producing a color filter that can be preferably applied in the present invention include Japanese Unexamined Patent Application Publication Nos. 2014-199272, 2013-064999, 2013-0664998, 2013-0664993, and 2013-054081.
  • Post-baking is a heat treatment after development for complete curing.
  • the heating temperature is preferably 250 ° C. or lower, more preferably 240 ° C. or lower, further preferably 230 ° C. or lower, and particularly preferably 220 ° C. or lower.
  • thermosetting treatment 50 ° C. or higher, and more preferably 100 ° C. or higher.
  • the pixels of the color filter may be cured by UV (ultraviolet) irradiation.
  • the film thickness of the cured film (color filter) is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, and particularly preferably 0.5 ⁇ m or more.
  • the size (pattern width) of the colored pattern (colored pixel) is preferably 5 ⁇ m or less, more preferably 4 ⁇ m or less, and particularly preferably 3 ⁇ m or less.
  • 0.1 ⁇ m or more is practical.
  • -Overcoat layer When using said color filter as a permanent film, it may have the process of forming an overcoat layer on a board
  • the overcoat layer for example, International Publication No. 2010/010899, Japanese Patent No. 4269480, Japanese Patent Application Laid-Open No. 2005-227525, Japanese Patent Application Laid-Open No. 2000-250217, Japanese Patent Application Laid-Open No. 9-221602, and This can be carried out using an epoxy-based radiation-sensitive resin composition (overcoat-forming composition) based on Japanese Unexamined Patent Publication No. 2001-343748.
  • specific examples of the process of forming the overcoat layer will be shown.
  • an epoxy-based radiation-sensitive resin composition is applied to the surface of the substrate and pre-baked to remove the solvent, thereby forming a film.
  • a coating method of the composition solution for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, and an ink jet method can be employed.
  • the spin coating method or the slit die coating method is particularly preferable.
  • the prebaking conditions vary depending on the type of each component, the blending ratio, etc., but are usually about 80 to 120 ° C. for about 1 to 15 minutes.
  • a silicon nitride substrate is preferably used as the substrate.
  • the pre-baked film is exposed and polymerized through a mask having a predetermined pattern, and then developed with a developing solution, and unnecessary portions are removed to form a pattern.
  • radiation used for exposure radiation such as visible light, ultraviolet light, far ultraviolet light, charged particle beam, and X-ray can be appropriately selected and used, but radiation having a wavelength in the range of 190 to 450 nm. Is preferred.
  • the developing method for example, any of a liquid filling method, a dipping method, a shower method, and the like may be used.
  • the development time is usually about 30 to 180 seconds at room temperature.
  • Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; diethylamine, And secondary amines such as di-n-propylamine; tertiary amines such as trimethylamine, methyldiethylamine, ethyldimethylamine, and triethylamine; tertiary alkanolamines such as dimethylethanolamine, methyldiethanolamine, and triethanolamine Pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, etc.
  • inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasi
  • Aromatic tertiary amines such as gin, collidine, lutidine, and quinoline; use of aqueous solutions (alkaline aqueous solutions) of alkaline compounds such as quaternary ammonium compounds such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. it can.
  • a water-soluble organic solvent such as methanol and ethanol and / or a surfactant can be added to the alkaline aqueous solution.
  • the pattern is heated by a heating device such as a hot plate and an oven at a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, for 3 to 10 minutes on the hot plate, and for example, 30 to 90 minutes in the oven.
  • a heating device such as a hot plate and an oven at a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, for 3 to 10 minutes on the hot plate, and for example, 30 to 90 minutes in the oven.
  • post-bake an overcoat layer can be obtained.
  • the treatment liquid of the present invention is applied during or after the production of a semiconductor substrate product.
  • a portion resist or permanent film
  • the substrate can be regenerated by removing a portion that needs to be repaired.
  • the method for regenerating a substrate of the present invention removes the permanent film or resist film provided on the substrate with the treatment liquid of the present invention during or after the manufacture of the semiconductor substrate product, thereby removing the above-mentioned semiconductor substrate product from the semiconductor substrate product. It includes a step of obtaining a substrate from which the permanent film or resist film has been removed.
  • the treatment liquid of the present invention can also be applied to cleaning and removing dry etching residue or dry ashing residue adhering to the substrate.
  • the cleaning removal method using the processing liquid of the present invention includes a cleaning step of cleaning at least one of a dry etching residue and a dry ashing residue adhered on the substrate with the processing liquid.
  • the composition is not particularly limited, water and, A hydrophilic organic solvent, A quaternary ammonium salt, 0.001 mass ppt to 1 mass ppm of inorganic anions with respect to the total mass of the treatment liquid, Further, at least one embodiment selected from the following (1) to (3) is preferable.
  • the treatment liquid further contains an amine compound.
  • the treatment liquid further contains a corrosion inhibitor.
  • the treatment liquid contains a water-soluble alcohol solvent as the hydrophilic organic solvent.
  • the treatment liquid When applying the treatment liquid of the present invention to cleaning and removing residues, the treatment liquid may be an aqueous treatment liquid or an organic solvent treatment liquid. When a residue contains an organic substance, it is preferable to use an organic solvent treatment liquid.
  • the substrate to be cleaned in the cleaning process is not particularly limited as long as a dry etching residue and a dry ash residue are attached, and a known substrate such as a substrate including the circuit structure described above can be processed. .
  • the substrate to which the dry etching residue and the dry ash residue adhere is specifically the surface or internal metal film by providing a hole, a pad pattern, or a wiring through a dry etching process (for via). And a substrate exposed.
  • the treatment liquid of the present invention can remove the residue without corroding the metal film disposed on the substrate.
  • the method of bringing the treatment liquid into contact with the substrate is not particularly limited.
  • the method of immersing the substrate in the treatment liquid placed in the tank, the method of spraying the treatment liquid on the substrate, the method of flowing the treatment liquid on the substrate, or Any combination thereof may be mentioned.
  • a method of immersing the substrate in the treatment liquid is preferable.
  • the temperature of the treatment liquid is preferably 90 ° C. or less, more preferably 25 to 80 ° C., further preferably 30 to 75 ° C., and particularly preferably 40 to 65 ° C.
  • the cleaning time can be adjusted according to the cleaning method used and the temperature of the treatment liquid.
  • the cleaning time is, for example, within 60 minutes, and preferably 1 to 60 minutes. It is more preferably 3 to 20 minutes, and further preferably 4 to 15 minutes.
  • the cleaning time is, for example, 10 seconds to 5 minutes, preferably 15 seconds to 4 minutes, more preferably 15 seconds to 3 minutes, and more preferably 20 seconds to More preferably, it is 2 minutes.
  • a mechanical stirring method may be implemented in order to further improve the cleaning ability of the treatment liquid.
  • the mechanical stirring method include a method of circulating the processing liquid on the substrate, a method of flowing or spraying the processing liquid on the substrate, and stirring by ultrasonic waves or megasonic.
  • the supply rate of the treatment liquid is preferably 0.05 to 5 L / min, and more preferably 0.1 to 3 L / min. By setting it as the said numerical range, it is excellent by the effect of this invention. Furthermore, it is possible to secure stable performance during continuous processing while ensuring better uniformity within the surface to be processed.
  • the chemical solution supply rate is 0.05 to 5 L / min
  • the content of inorganic anions in the treatment solution is desirably 1 mass ppt or more.
  • a step of rinsing the substrate with a solvent and cleaning the substrate may be further included.
  • the rinsing step is preferably carried out continuously with the washing step, and is a rinsing step with a rinsing solvent for 5 seconds to 5 minutes.
  • the rinse process may implement the mechanical stirring method described above.
  • rinsing solvent examples include deionized (DI) water, methanol, ethanol, isopropyl alcohol, N-methylpyrrolidinone, ⁇ -butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. It is not limited to. Or you may utilize the aqueous
  • the rinsing solvent is preferably an aqueous ammonium hydroxide solution, DI water, methanol, ethanol, or isopropyl alcohol, more preferably an aqueous ammonium hydroxide solution, DI water, or isopropyl alcohol, and even more preferably an aqueous ammonium hydroxide solution or DI water.
  • a method of bringing the rinsing solvent into contact with the substrate the above-described method of bringing the treatment liquid into contact with the substrate can be similarly applied.
  • the temperature of the rinsing solvent in the rinsing step is preferably 16 to 27 ° C.
  • the drying method is not particularly limited. Examples of the drying method include spin drying, a method of allowing a dry gas to flow over a substrate with a mask, a method of heating a substrate by a heating means such as a hot plate or an infrared lamp, Marangoni drying, rotagoni drying, IPA (isopropyl alcohol). ) Drying, or any combination thereof.
  • the drying time depends on the specific method used, but is generally preferably 30 seconds to several minutes.
  • the treatment liquid of the present invention can be applied as a rinsing liquid in the rinsing process described above.
  • the treatment liquid may be an aqueous treatment liquid or an organic solvent treatment liquid, but it is preferable to use an aqueous treatment liquid from the viewpoint that a residue is less likely to remain in subsequent steps.
  • the treatment liquid of the present invention can also be applied as a silicon etching liquid for a polycrystalline silicon film or an amorphous silicon film.
  • a silicon etching liquid for a polycrystalline silicon film or an amorphous silicon film can also be used as an etching solution for forming a capacitor structure having an uneven shape to be a capacitor.
  • it can also be used for the silicon etching solution described in US Patent Application Publication No. 2007/0175862, Japanese Unexamined Patent Application Publication No. 2014-220300, and Japanese Unexamined Patent Application Publication No. 2013-008900.
  • the composition is not particularly limited, water and, A hydrophilic organic solvent, A quaternary ammonium salt, 0.001 mass ppt to 1 mass ppm of inorganic anions with respect to the total mass of the treatment liquid, Furthermore, it is preferable that it is at least 1 sort (s) chosen from following (1) and (2).
  • the treatment liquid further contains an amine compound.
  • a water-soluble alcohol solvent is included as the hydrophilic organic solvent.
  • the etching solution water and, A hydrophilic organic solvent, A quaternary ammonium salt, 0.001 mass ppt to 1 mass ppm of inorganic anions with respect to the total mass of the treatment liquid, Furthermore, the aspect containing an oxidizing agent is preferable.
  • the treatment liquid further contains a corrosion inhibitor.
  • the treatment liquid further contains an amine compound.
  • the treatment liquid further contains a chelating agent.
  • a phosphonic acid chelating agent having a hydroxyl group and a phosphonic acid chelating agent having a hydroxyl group described in JP 2012-080128 A Two or more kinds of anionic species other than those having no oxidizing power may be used in combination.
  • the treatment liquid of the present invention When the treatment liquid of the present invention is applied to the etching liquid, the treatment liquid may be an aqueous treatment liquid or an organic solvent treatment liquid.
  • an aqueous processing solution is more advantageous from the viewpoint of etching speed. What was mentioned above can be used for said amine compound and water-soluble alcohol solvent.
  • the semiconductor wafer for etching a polycrystalline silicon film or an amorphous silicon film as described above is not particularly limited, but a semiconductor wafer having a group IV material such as SiP and SiGe on a silicon substrate. can give.
  • the treatment solution of the present invention Al, Cu, a metal electrode layer such as W, Co, HfO, HfSiO, WO, AlO x, SiO 2, SiOC, SiON, SiOCN, TiN, SiN, and an insulating film such as TiAlC Since damage and elution of the layer can also be suitably suppressed, it is also preferable to be applied to a semiconductor substrate including these.
  • composition of a metal compound when expressed by a combination of elements, it means that a composition having an arbitrary composition is widely included.
  • SiOC SiON
  • each treatment liquid of Examples and Comparative Examples were purified by the method described in JP-A-2007-254168, and both contained inorganic anions in the liquid. After confirming that the amount was less than 0.001 mass ppt, it was used for adjusting the treatment liquid.
  • the amount of inorganic anions contained in the liquid was analyzed by an ion chromatography method (DX-500, manufactured by Nippon Dionex Co., Ltd.). All analytical measurements were performed in a clean room that meets ISO class 2 or lower. In order to improve the measurement accuracy, the measurement of the treatment liquid with the inorganic anion content of 0.001 mass ppt (corresponding to 1 mass ppq in the table described later) is concentrated to 1/100 in terms of volume. And the content of the inorganic anion was calculated in terms of the concentration of the treatment liquid before concentration.
  • DX-500 ion chromatography method
  • TMAH Tetramethylammonium hydroxide (manufactured by SACHEM)
  • TEAH Tetraethylammonium hydroxide (manufactured by SACHEM)
  • TBAH Tetrabutylammonium hydroxide (manufactured by SACHEM)
  • AH212 Dimethylbis (2-hydroxyethyl) ammonium hydroxide (Yokkaichi Synthesis)
  • DMSO Dimethyl sulfoxide (Wako Pure Chemical Industries, Ltd.) Diethylene glycol monoethyl ether (Wako Pure Chemical Industries, Ltd.) Propylene glycol (Wako Pure Chemical Industries, Ltd.) Sulfolane (also known as tetrahydrothiophene 1,1-dioxide) (Wako Pure Chemical Industries, Ltd.) Hydroxylamine (BASF) Alkanolamine (using diglycolamine) (manufactured by Tokyo Chemical Industry Co., Ltd.) Surfynol MD-20 (manu
  • inorganic anions in each treatment solution were introduced by containing nitric acid, hydrochloric acid, and sulfuric acid as ion sources so as to have concentrations shown in the table.
  • Red Pigment Dispersion 2 As a pigment, C.I. I. Pigment Red 254 12.1 parts, BYK2001 (Disperbyk: manufactured by BYK) (solid content concentration 45.1% by mass) as a dispersant, 10.4 parts, and benzyl methacrylate / methacrylic acid copolymer (as a dispersion resin)
  • composition A Pigment dispersion (any of pigment dispersions 1 to 3 above) 82.35 parts Alkali-soluble resin 2.05 parts Polymerization initiator 1.2 parts DPHA (polymerizable compound) 1.4 parts M-305 (polymerizable compound) ) 1.4 parts p-methoxyphenol 0.001 part PEGMEA 7.4 parts F-1 4.2 parts
  • composition A Each component contained in the composition A is as follows. Polymerization initiator: IRGACURE OXE01 [trade name] manufactured by BASF DPHA: Nippon Kayaku Co., Ltd. KARAYAD DPHA [trade name] Dipentaerythritol hexaacrylate M-305: A mixture of triacrylate and pentaerythritol tetraacrylate manufactured by Toagosei Co., Ltd. [trade name] F-1: A mixture represented by the following formula was applied as a 0.2% solution of PEGMEA.
  • PEGMEA Propylene glycol monomethyl ether acetate
  • GPC gel permeation chromatography
  • the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).
  • the exposure amount is changed by 50 mJ / cm 2 ).
  • the silicon wafer on which the irradiated coating film was disposed was placed on a horizontal rotary table of a spin shower developing machine (DW-30 type; manufactured by Chemtronics). Paddle development was performed at 23 ° C. for 180 seconds using a 40% dilution of CD-2000 (manufactured by FUJIFILM Electronics Materials) to form a colored pattern on the silicon wafer.
  • the silicon wafer on which the colored pattern was formed was fixed to the horizontal rotary table by a vacuum chuck method.
  • Al blanket wafer An aluminum (Al) layer was formed on another silicon wafer by a chemical vapor deposition (CVD) method to obtain an Al blanket wafer.
  • the thickness of Al was about 0.5 ⁇ m.
  • ⁇ Implementation of color filter peeling test and Al corrosion prevention test Using each processing solution described in Tables 1 and 2, a color filter peeling test and an Al corrosion prevention test were performed according to the following procedure.
  • the silicon wafer and the Al blanket wafer on which the color filter was arranged were cut into 1 ⁇ 2 cm to obtain two types of test wafers (test wafer with color filter, test wafer with Al).
  • the stirrer and the treatment liquid were placed in a beaker and heated to 70 ° C. while stirring the treatment liquid at a rotational speed of 250 rpm. Thereafter, the test wafer was immersed for 5 minutes. Thereafter, the test wafer was taken out of the processing liquid, and ion exchange water (DIW) was ejected from the two-fluid nozzle onto the test wafer and rinsed for 30 seconds.
  • DIW ion exchange water
  • Evaluation of corrosion resistance of Al is based on the film slip amount (%) calculated from the film thickness of the Al layer before and after the treatment of ⁇ color filter peeling test and Al corrosion prevention test> on a test wafer with Al. Based on.
  • the film thickness was calculated from the current value of the Al layer using a four-terminal ammeter (trade name VR200, manufactured by Kokusai Electric Alpha Co., Ltd.).
  • Y Film thickness after treatment of test wafer with Al after the above-mentioned treatment (nm)
  • the evaluation criteria are as follows.
  • A The amount of film slip is 5% or less.
  • B The amount of film slip is more than 5% and 10% or less.
  • C The amount of film slip is more than 10% and 50% or less.
  • D The amount of film slip is over 50%.
  • Examples A37, A38, and A39 a treatment solution was prepared and evaluated in the same manner except that hydroxylamine was changed to hydroxylamine sulfate (manufactured by Aldrich, 99.999% trace metals bases). The same results as in Examples A37, A38, and A39 were obtained.
  • Example A107 has a removability of “A”, but compared with Example A2. There was a lot of residue.
  • Example A108 although the removability was “A”, the amount of the residue was larger than that in Example A3.
  • Example A109 although the removability was “A”, the amount of the residue was larger than that in Example A4. That is, it was confirmed that the effect of the present invention is more excellent when the water content in the organic solvent-based treatment liquid is 1% by mass or more.
  • Examples A112, A113, and A114 had a removability of “A”, but some residue was confirmed. On the other hand, it was confirmed that the residue can be reduced when the content of DMSO in each of the treatment liquids of Examples A112, A113, and A114 is 1% by mass or more. That is, when it was set as the aqueous processing liquid, when content of the hydrophilic organic solvent was 1 mass% or more, it was confirmed that the effect of this invention is more excellent.
  • the treatment liquid of the comparative example did not exhibit the desired effect because the content of inorganic anions with respect to the total mass of the treatment liquid was not within the predetermined range.
  • a multilayer substrate (corresponding to a pre-treatment multilayer substrate) is provided on a Si substrate with a wiring film composed of an Al alloy film and a titanium nitride film, a silicon oxide film, and a resist film having a predetermined opening in this order. ) was formed.
  • the laminated substrate 10 having the above was manufactured as a workpiece sample (pattern wafer) (see FIG. 1).
  • the prepared pattern wafer section (about 2.0 cm ⁇ 2.0 cm) is immersed in each cleaning composition heated to 70 ° C. for 15 minutes, and then the pattern wafer section is taken out and immediately washed with ultrapure water. Water separation and N 2 drying were performed.
  • the surface of the section of the patterned wafer after the immersion test is observed with an SEM, according to the following evaluation criteria for the removal property of the dry etching residue and the ashing residue, and the corrosion resistance of Al of the wiring exposed at the bottom of the hole 6 Evaluation was performed. The evaluation criteria are shown below.
  • Residue removability (removability)> “A”: The residue was completely removed or less than 25% of the residue remained. “B”: The dissolution of the residue was incomplete, and 25% or more and 50% or less of the residue remained. “C”: More than 50% of the residue remained.
  • A The amount of film slip is 5% or less.
  • B The amount of film slip is more than 5% and 10% or less.
  • C The amount of film slip is more than 10% and 50% or less.
  • D The amount of film slip is over 50%.
  • Example B112 is compared with Example B2, although the removability is “A”. There was a lot of residue.
  • Example B113 although the removability was “A”, the amount of the residue was larger than that in Example B3.
  • Example B114 although the removability was “A”, the amount of the residue was larger than that in Example B4.
  • the effect of the present invention was more excellent when the hydrophilic organic solvent was 1% by mass or more.
  • Examples B107, B108, and B109 were confirmed to have a slight amount of residue although the removability was “A”.
  • the DMSO content in each of the treatment liquids of Examples B107, B108, and B109 was reduced so that the water content was 1% by mass or more, the residue could be reduced. That is, when it was set as the organic solvent processing liquid, when the content of water was 1% by mass or more, it was confirmed that the effect of the present invention was more excellent.
  • the treatment liquid of the present invention has excellent corrosion removal properties for dry etching residues and dry ashing residues while having corrosion resistance to metal films. confirmed.
  • the treatment liquid of the comparative example did not exhibit the desired effect because the content of inorganic anions with respect to the total mass of the treatment liquid was not within the predetermined range.
  • Test wafer A poly-Si wafer having a thickness of 500 nm formed on a single crystal ⁇ 100> silicon was prepared. On the other hand, the dry etching process was performed. Subsequently, the poly-Si wafer was subjected to a cleaning process under the following conditions using a single wafer type apparatus (manufactured by SPS-Europe BV, POLOS (trade name)), and an evaluation test was performed. ⁇ Chemical temperature: 60 °C ⁇ Discharge rate: 1 L / min.
  • a SiN film was formed on Poly-Si by CVD (chemical vapor deposition), a photoresist film was formed, and the photoresist was patterned by UV (ultraviolet) exposure and development to produce a resist film. Thereafter, the SiN film was dry-etched with a fluorine-based gas, and the obtained substrate was used as an evaluation target. The obtained substrate was immersed in each treatment solution described in Table 5 adjusted to 60 ° C., and treated for 30 seconds. Thereafter, the substrate was taken out from each processing solution, washed with water, and further dried by air blowing.
  • ⁇ Electrode corrosion prevention> A model substrate having SiP and SiGe as electrodes formed by CVD was used as an evaluation target. The obtained substrate was immersed in each treatment solution described in Table 5 adjusted to 60 ° C., and treated for 30 seconds. Thereafter, the substrate was taken out from each processing solution, washed with water, and further dried by air blowing. In the following evaluation criteria, the “film slip amount” was determined by the same method as in the above ⁇ Evaluation of Al corrosion prevention>.
  • A film slippage amount is 5% or less.
  • B The amount of film slip is more than 5% and 20% or less.
  • C The amount of film slippage exceeds 20%.
  • A film slippage amount is 5% or less.
  • B The amount of film slip is more than 5% and 20% or less.
  • C The amount of film slippage exceeds 20%.
  • the chemical supply rate is preferably 0.05 to 5 L / min.
  • Example A2 when the content of the inorganic anion was 1 mass ppq to 1 mass ppm, the evaluation was “A” at any flow rate.
  • the chemical supply rate exceeds 5.5 L / min, the chemical supply rate is 0.05 L / min and Compared to the case of 3 L / min, the residue removal property against Poly-Si and the corrosion prevention property against SiP and SiGe were slightly inferior.

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  • Cleaning Or Drying Semiconductors (AREA)
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  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

La présente invention concerne le problème de préparation d'une solution de traitement qui confère des propriétés de prévention de la corrosion à un film métallique disposé sur un substrat, et qui fait preuve d'une excellente aptitude au retrait d'un film organique sur un substrat ou aptitude au retrait d'un résidu de gravure sec ou d'un résidu de cendre sec qui adhère au substrat. Cette solution de traitement comprend de l'eau, un solvant organique hydrophile, un sel d'ammonium quaternaire, et un anion inorganique, la teneur de l'anion inorganique est de 0,001 ppt en masse à 1 ppm en masse par rapport à la masse totale de la solution de traitement.
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JP2023152278A (ja) * 2022-03-31 2023-10-16 株式会社片山化学工業研究所 洗浄剤
WO2023244825A1 (fr) * 2022-06-16 2023-12-21 Entegris, Inc. Procédé de gravure du polysilicium
JP2025519682A (ja) * 2022-06-16 2025-06-26 インテグリス・インコーポレーテッド ポリシリコンをエッチングするための方法
WO2024048498A1 (fr) * 2022-09-01 2024-03-07 株式会社トクヤマ Liquide de gravure de silicium, procédé permettant de traiter un substrat et procédé permettant de produire un dispositif au silicium
WO2025235712A1 (fr) * 2024-05-08 2025-11-13 Essex Solutions Usa Llc Mélanges de solvants alternatifs à utiliser dans la formation et l'application de polyamide-imide thermodurcissable

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KR102113463B1 (ko) 2020-05-21
JP6646073B2 (ja) 2020-02-14

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