WO2021039701A1 - Liquide de traitement - Google Patents

Liquide de traitement Download PDF

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Publication number
WO2021039701A1
WO2021039701A1 PCT/JP2020/031798 JP2020031798W WO2021039701A1 WO 2021039701 A1 WO2021039701 A1 WO 2021039701A1 JP 2020031798 W JP2020031798 W JP 2020031798W WO 2021039701 A1 WO2021039701 A1 WO 2021039701A1
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Prior art keywords
treatment liquid
mass
metal
content
metal ion
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PCT/JP2020/031798
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English (en)
Japanese (ja)
Inventor
祐継 室
篤史 水谷
智威 高橋
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富士フイルム株式会社
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Publication of WO2021039701A1 publication Critical patent/WO2021039701A1/fr

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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
    • C11D7/10—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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/16—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions using inhibitors
    • C23G1/18—Organic inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting

Definitions

  • the present invention relates to a treatment liquid.
  • the present invention relates to a treatment liquid that can be suitably used for manufacturing a semiconductor device.
  • Semiconductor devices such as CCD (Charge-Couple Device) and memory are manufactured by forming fine electronic circuit patterns on a substrate using photolithography technology. Specifically, a resist film is formed on a laminate having a metal film as a wiring material, an etching stop layer, and an interlayer insulating layer on a substrate, and a photolithography step and a dry etching step (for example, plasma etching treatment). By carrying out the above, a semiconductor device is manufactured.
  • CCD Charge-Couple Device
  • memory are manufactured by forming fine electronic circuit patterns on a substrate using photolithography technology. Specifically, a resist film is formed on a laminate having a metal film as a wiring material, an etching stop layer, and an interlayer insulating layer on a substrate, and a photolithography step and a dry etching step (for example, plasma etching treatment).
  • metal material-based resist films such as TiN and AlOx (so-called metal hard masks) are also used as the resist films.
  • a dry etching process for example, plasma etching treatment
  • a step of exposing the metal film surface to be a film is performed.
  • the substrate that has undergone the dry etching step contains a large amount of dry etching residue (when a metal hard mask is used as the resist film, a large amount of metal components such as titanium-based metals are contained as residue components. On the other hand, a photoresist film is used. In some cases, a large amount of organic components are contained as residual components). These residues are generally removed using a treatment liquid so as not to interfere with the next step.
  • Patent Document 1 states that "at least selected from the group consisting of hydroxyamine and 1,8-diazabicyclo [5.4.0] undecene-7 and 1,4-diazabicyclo [2.2.2] octane.
  • a cleaning solution for lithography containing one amine compound, a water-soluble organic solvent, and water and having a pH of 8 or more, and containing the water-soluble organic solvent in an amount of 10% by mass or more based on the total amount of the cleaning solution for lithography.
  • a cleaning solution for lithography which is characterized by the above, is disclosed.
  • the present inventors examined the time-dependent performance of the treatment liquid described in Patent Document 1, they found that the performance stability may be inferior when stored under predetermined conditions. More specifically, in general, the treatment liquid is refrigerated at a predetermined temperature when not in use, and when in use, the treatment liquid is taken out of the refrigeration storage and returned to room temperature for use. The present inventors repeatedly performed a series of operations in which the treatment liquid was refrigerated for a predetermined time and then allowed to stand at room temperature for a predetermined time, and the residue removing performance of the treatment liquid (particularly, metal hard).
  • the mask-derived residue removal performance) and the anticorrosion performance may be inferior, and the stability of these performances may be inferior. That is, it was clarified that there is room for improving the treatment liquid so that the residual removal performance and the anticorrosion performance are ensured even if the temperature environment changes as described above. In the following, ensuring the above performance is also referred to as being excellent in performance stability of residue removing performance and anticorrosion performance.
  • the present invention has a residue removing performance (particularly, a metal hard mask-derived residue removing performance) and an anticorrosion performance (particularly, an anticorrosion performance against a Co or Co alloy) even if the temperature environment changes such as refrigerated storage and room temperature standing are repeated. ), It is an object of the present invention to provide a treatment liquid having excellent performance stability.
  • Hydroxylamine compounds selected from the group consisting of hydroxyamines and hydroxyamine salts, and With organic solvent Basic compounds and A treatment liquid containing one or more first metal ions selected from the group consisting of Na, Al, K, Ca, Cr, Fe, Ni, and Zn.
  • a treatment liquid in which the total content of the first metal ions is 7.0 mass ppb to 800.0 mass ppb with respect to the total mass of the treatment liquid.
  • the content of at least one metal ion among the first metal ions contained in the treatment liquid is 1.0 mass ppb to 100.0 mass ppb with respect to the total mass of the treatment liquid. , [1].
  • the first metal ions contained in the treatment liquid are two or more kinds, and the content of each metal ion is 1.0 mass ppb to 100. With respect to the total mass of the treatment liquid.
  • the content of at least one metal ion among the second metal ions contained in the treatment liquid is 0.01 mass ppb to 1.0 mass ppb with respect to the total mass of the treatment liquid.
  • the number of the second metal ions contained in the treatment liquid is two or more, and the content of each metal ion is 0.01 mass ppb to 1. with respect to the total mass of the treatment liquid.
  • the present invention it is possible to provide a treatment liquid having excellent performance stability of residue removal performance and anticorrosion performance even if the temperature environment changes such as refrigerated storage and room temperature standing are repeated.
  • the numerical range represented by using "-” means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the term “preparation” includes not only synthesizing or blending a specific material to prepare the material, but also procuring a predetermined material by purchase or the like.
  • ppb means "parts-per-parts ( 10-9 )”.
  • 1 ⁇ (angstrom) corresponds to 0.1 nm.
  • notations that do not describe substitutions and non-substitutions include those that do not have substituents and those that have substituents as long as the effects of the present invention are not impaired. It includes.
  • the "hydrocarbon group” includes not only a hydrocarbon group having no substituent (unsubstituted hydrocarbon group) but also a hydrocarbon group having a substituent (substituted hydrocarbon group). .. This is synonymous with each compound.
  • the pH of the treatment liquid is a value measured by F-51 (trade name) manufactured by HORIBA, Ltd. at room temperature (25 ° C.).
  • the "radiation” in the present invention means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
  • light means active light rays or radiation.
  • exposure refers not only to exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays or EUV light, but also for drawing with particle beams such as electron beams or ion beams. Include in exposure.
  • the treatment liquid of the present invention is Hydroxylamine compounds selected from the group consisting of hydroxyamines and hydroxyamine salts, and With organic solvent Basic compounds and A treatment liquid containing one or more first metal ions selected from the group consisting of Na, Al, K, Ca, Cr, Fe, Ni, and Zn.
  • the total content of the first metal ions is 7.0 mass ppb to 800.0 mass ppb with respect to the total mass of the treatment liquid.
  • the above-mentioned treatment liquid can be applied as a treatment liquid for a semiconductor device to each process when manufacturing a semiconductor device.
  • the treatment liquid can be suitably used as a cleaning liquid after a dry etching step using a metal hard mask as a mask.
  • the treatment liquid of the present invention contains a hydroxyamine compound selected from the group consisting of hydroxyamines and hydroxyamine salts.
  • the hydroxyamine compound has a function of promoting decomposition and solubilization of the residue.
  • the "hydroxyamine” according to the hydroxyamine compound of the treatment liquid of the present invention refers to a hydroxyamine compound in a broad sense including a substituted or unsubstituted alkylhydroxyamine, and any of them is the present invention.
  • the effect of can be obtained.
  • the hydroxyamine compound is not particularly limited, but as a preferred embodiment, an unsubstituted hydroxyamine and a hydroxyamine derivative, and a salt thereof are preferable.
  • the hydroxyamine derivative is not particularly limited, but for example, O-methylhydroxyamine, O-ethylhydroxyamine, N-methylhydroxyamine, N, N-dimethylhydroxyamine, N, O-dimethylhydroxyamine, N-ethylhydroxy.
  • the inorganic acid salt or the organic acid salt of the above-mentioned unsubstituted hydroxyamine or the hydroxyamine derivative is preferable, and a non-metal atom such as Cl, S, N, or P is a hydrogen atom.
  • a salt of an inorganic acid formed by binding with is more preferable, and a salt of any of hydrochloric acid, sulfuric acid, and nitric acid is further preferable.
  • hydroxyamine nitrate hydroxyamine nitrate
  • hydroxyamine sulfate hydroxyamine sulfate
  • hydroxyamine hydrochloride hydroxyamine phosphate, N, N-diethylhydroxyamine sulfate, N, N-diethylhydroxyamine nitrate, or A mixture of these is preferred.
  • examples of the above-mentioned organic acid salt of the unsubstituted hydroxyamine or the hydroxyamine derivative include hydroxyammonium citrate, hydroxyammonium oxalate, and hydroxyammonium fluoride.
  • hydroxyamine compound at least one hydroxyamine compound selected from the group consisting of hydroxyamine and hydroxyamine sulfate is preferable in that the residue removing performance of the treatment liquid and the anticorrosion performance over time are more excellent. Unsubstituted hydroxyamines and sulfates thereof are more preferred, and unsubstituted hydroxyamines are even more preferred.
  • the lower limit of the content of the hydroxyamine compound is preferably 0.1% by mass or more with respect to the total mass of the treatment liquid, and is 1% by mass or more in that the residue removal property and defect suppression property of the treatment liquid are more excellent. Is more preferable, and 3% by mass or more is further preferable.
  • the upper limit of the content of the hydroxyamine compound is preferably 40% by mass or less, more preferably 30% by mass or less, and 25% by mass, because the anticorrosion performance of the treatment liquid is more excellent with respect to the total mass of the treatment liquid. The following is more preferable, 20% by mass or less is particularly preferable, and 15% by mass or less is most preferable.
  • the hydroxyamine compound may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably within the above range.
  • the treatment liquid of the present invention contains a basic compound.
  • the "basic compound” referred to here and the above-mentioned hydroxyamine compound are different compounds. That is, the hydroxyamine compound is not included in the basic compound.
  • the basic compound may be either an inorganic base compound or an organic base compound, but an organic basic compound is preferable in that the treatment liquid has more excellent residue removing property and defect suppressing property, and an amine compound or a nitrogen-containing compound is preferable. Aromatic compounds are more preferred.
  • an amine compound having a cyclic structure is preferable.
  • the amino group may be present in only one of the cyclic structure and the outside of the cyclic structure, or may be present in both.
  • the amino group is a tertiary amino group
  • the tertiary amino group is present in the cyclic structure
  • the cyclic structure is a non-aromatic cyclic structure (nitrogen-containing non-aromatic ring).
  • amine compound examples include tetrahydrofurfurylamine, N- (2-aminoethyl) piperazine, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), and 1,4-diazabicyclo [2.2].
  • DBU 1,8-diazabicyclo [5.4.0] -7-undecene
  • amine compound examples include tetrahydrofurfurylamine, N- (2-aminoethyl) piperazine, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), and 1,4-diazabicyclo [2.2].
  • DBU 1,8-diazabicyclo [5.4.0] -7-undecene
  • .2] Octane, hydroxyethylpiperazine, piperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, cis-2,6-dimethylpiperazine, 2-piperidine
  • tetrahydrofurfurylamine and N are used as amine compounds from the viewpoint of more effectively suppressing the corrosion of the metal layer (preferably the metal layer containing Co or Co alloy) on the substrate while ensuring the residue removing performance.
  • -(2-Aminoethyl) piperazin, 1,8-diazabicyclo [5.4.0] -7-undecene, or 1,4-diazabicyclo [2.2.2] octane is preferred.
  • the molecular weight of the amine compound is preferably 50 to 500, more preferably 75 to 400, and even more preferably 100 to 300.
  • the nitrogen-containing aromatic compound is not particularly limited, and for example, substituted or unsubstituted benzotriazole is preferable.
  • substituted benzotriazole for example, a benzotriazole substituted with an alkyl group or an aryl group is preferable.
  • Specific examples of the substituted or unsubstituted benzotriazole include benzotriazole (BTA) and 5-methyl-1H-benzotriazole (5M-BTA).
  • the basic compound may be used alone or in combination of two or more.
  • the content of the basic compound (the total content when two or more kinds are used) is, for example, 0.1 to 20% by mass and 0.5 to 15% by mass with respect to the total mass of the treatment liquid. preferable.
  • the treatment liquid of the present invention contains an organic solvent.
  • the organic solvent is not particularly limited, but an alcohol solvent is preferable, and a water-soluble alcohol solvent is more preferable.
  • the alcohol-based solvent include alkanediols, alkylene glycols, alkoxy alcohols, saturated aliphatic monohydric alcohols, unsaturated non-aromatic monohydric alcohols, and trihydric or higher alcohols.
  • alkanediol examples include glycol, 2-methyl-1,3-propanediol, 1,2-propanezyl, 1,3-dihydroxypropane, 2-methylpentane-2,4-diol, and 2,2-dimethyl.
  • alkylene glycol examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol and the like.
  • alkoxy alcohol examples include 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 1-methoxy-2-butanol, glycol monoether and the like.
  • glycol monoether examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monon-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether (EGBE), diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether.
  • Saturated aliphatic monohydric alcohols include, for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, t-pentyl alcohol, and 1-Hexanol and the like can be mentioned.
  • unsaturated non-aromatic monohydric alcohols examples include allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, 4-pentene-2-ol and the like.
  • low molecular weight alcohols containing a ring structure examples include tetrahydrofurfuryl alcohol, furfuryl alcohol, and 1,3-cyclopentanediol.
  • trihydric or higher alcohols examples include glycerin and the like.
  • alkanediol preferably 2-methylpentane-2,4-diol
  • alkoxyalcohol preferably 3-methoxy-3-methylbutanol
  • glycol monoether preferably, preferably) EGBE
  • the molecular weight of the organic solvent is preferably 32 to 250, more preferably 40 to 200, and even more preferably 50 to 150.
  • the lower limit of the content of the organic solvent is preferably 1% by mass or more with respect to the total mass of the treatment liquid, and more preferably 2% by mass or more in that the residue removal performance and the anticorrosion performance are more excellent over time. ..
  • the upper limit of the content of the organic solvent is preferably 40% by mass or less with respect to the total mass of the treatment liquid, and more preferably 30% by mass or less in that the residue removal performance and the anticorrosion performance are more excellent over time. , 25% by mass or less is more preferable.
  • the organic solvent may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably within the above range.
  • the treatment liquid of the present invention contains one or more first metal ions selected from the group consisting of Na, Al, K, Ca, Cr, Fe, Ni, and Zn.
  • the lower limit of the total content of the first metal ions in the treatment liquid of the present invention is 7.0 mass ppb or more with respect to the total mass of the treatment liquid, and the stability over time of the residue removal performance and the anticorrosion performance is good. In terms of superiority, 8.0 mass ppb or more is preferable, and 9.0 mass ppb or more is more preferable.
  • the upper limit of the total content of the first metal ion is 800.0 mass ppb or less with respect to the total mass of the treatment liquid, and 700 in that the residue removal performance and the anticorrosion performance are more excellent over time. It is preferably 0.0 mass ppb or less, and more preferably 600.0 mass ppb or less.
  • the content of at least one metal ion among the first metal ions contained in the treatment liquid is 1. With respect to the total mass of the treatment liquid, in that the residue removal performance and the anticorrosion performance are more excellent over time. It is preferably 0 to 100.0 mass ppb.
  • the treatment liquid contains two or more first metal ions, and the content of each metal ion is the total mass of the treatment liquid. It is preferably 1.0 to 100.0 mass ppb, and the treatment liquid is all selected from the group consisting of Na, Al, K, Ca, Cr, Fe, Ni, and Zn as the first metal ion. It is more preferable that the metal ions of the above are contained and the content of each metal ion is 1.0 to 100.0 mass ppb with respect to the total mass of the treatment liquid.
  • the treatment liquid contains at least Ca ion as the first metal ion in that the residue removal performance and the anticorrosion performance are more excellent over time.
  • the first metal ion may be a metal ion inevitably contained in each component (raw material) contained in the treatment liquid, or a metal ion inevitably contained in the production, storage, and / or transfer of the treatment liquid. It may be added intentionally.
  • Examples of the method of intentionally adding the first metal ion to the system include a method of adding a metal salt containing the corresponding metal atom.
  • the type of the metal salt is not particularly limited, and examples thereof include sulfates, chloride salts, and bromide salts.
  • the type and content of metal ions in the treatment liquid can be measured by the SP-ICP-MS method (Single Nano Particile Inductively Coupled Plasma Mass Spectrometry).
  • the SP-ICP-MS method uses the same apparatus as the ordinary ICP-MS method (inductively coupled plasma mass spectrometry), and differs only in data analysis. Data analysis of the SP-ICP-MS method can be performed by commercially available software.
  • the content of the metal component to be measured is measured regardless of its existence form. Therefore, the total mass of the metal particles and the metal ions to be measured is quantified as the content of the metal component.
  • the content of metal particles can be measured. Therefore, the content of metal ions in the sample can be calculated by subtracting the content of the metal particles from the content of the metal component in the sample.
  • the device for the SP-ICP-MS method include an Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometery, option # 200) manufactured by Agilent Technologies, Inc., which is described in Examples. It can be measured by the above method.
  • the Agilent 8900 manufactured by Agilent Technologies can also be used.
  • the treatment liquid of the present invention preferably further contains water.
  • the content of water in the treatment liquid of the present invention is not particularly limited, and is preferably 15 to 98% by mass, more preferably 30 to 95% by mass, and further 50 to 95% by mass with respect to the total mass of the treatment liquid. preferable.
  • the treatment liquid of the present invention preferably further contains a second metal ion.
  • the second metal ion is one or more metal ions selected from the group consisting of Li, Mg, Mn, Cu, Ag, Pb, and Co.
  • the lower limit of the total content of the second metal ion in the treatment liquid of the present invention is preferably 0.01 mass ppb or more with respect to the total mass of the treatment liquid, and the stability over time of the residue removal performance and the anticorrosion performance is good. In terms of superiority, 0.05 mass ppb or more is more preferable, and 0.1 mass ppb or more is further preferable.
  • the upper limit of the total content of the second metal ion is preferably 10.0 mass ppb or less with respect to the total mass of the treatment liquid, and the residue removal performance and the anticorrosion performance are more excellent over time. It is more preferably 0.0 mass ppb or less, and further preferably 6.0 mass ppb or less.
  • the content of at least one metal ion among the second metal ions contained in the treatment liquid is 0, based on the total mass of the treatment liquid, in that the residue removal performance and the anticorrosion performance are more excellent over time. It is preferably 01 to 1.0 mass ppb.
  • the treatment liquid contains two or more types of second metal ions, and the content of each metal ion is the total mass of the treatment liquid. It is preferably 0.01 to 1.0 mass ppb, and all metals selected from the group consisting of Li, Mg, Mn, Cu, Ag, Pb, and Co as the second metal ion in the treatment liquid. More preferably, it contains ions and the content of each metal ion is 0.01 to 1.0 mass ppb with respect to the total mass of the treatment liquid.
  • the second metal ion may be a metal ion inevitably contained in each component (raw material) contained in the treatment liquid, or a metal ion inevitably contained in the production, storage, and / or transfer of the treatment liquid. It may be added intentionally.
  • Examples of the method of intentionally adding the second metal ion to the system include a method of adding a metal salt containing the corresponding metal atom.
  • the type of the metal salt is not particularly limited, and examples thereof include sulfates, chloride salts, and bromide salts.
  • the method for measuring the content of the second metal ion in the treatment liquid is the same as the method for measuring the content of the first metal ion described above.
  • the treatment liquid of the present invention preferably further contains a chelating agent.
  • the chelating agent chelate with the oxidized metal contained in the residue.
  • the chelating agent is not particularly limited, but a polyaminopolycarboxylic acid is preferable.
  • a polyaminopolycarboxylic acid is a compound having a plurality of amino groups and a plurality of carboxylic acid groups. Examples of the polyaminopolycarboxylic acid include mono- or polyalkylene polyamine polycarboxylic acids, polyaminoalkane polycarboxylic acids, polyaminoalkanol polycarboxylic acids, and hydroxyalkyl ether polyamine polycarboxylic acids.
  • polyaminopolycarboxylic acid examples include butylenediaminetetraacetic acid, diethylenetriaminetetraacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraminehexacetic acid, 1,3-diamino-2-hydroxypropane-N, N, N', N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid, ethylenediaminediaminetetraacetic acid, ethylenediaminediaminedipropionic acid, 1,6-hexamethylene-diamine-N, N , N', N'-tetraacetic acid, N, N-bis (2-hydroxybenzyl) ethylenediamine-N, N-diacetate, diaminopropanetetraacetic acid, 1,4,7,10-t
  • the content of the chelating agent in the treatment liquid of the present invention is not particularly limited, and is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, based on the total mass of the treatment liquid.
  • the chelating agent may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably within the above range.
  • the treatment liquid of the present invention may further contain other components other than the above-mentioned components.
  • other components include surfactants, quaternary ammonium hydroxide salts, reducing agents, pH adjusting agents, foodstuff-proofing agents, defoaming agents, rust-preventing agents, preservatives and the like.
  • the pH of the treatment liquid of the present invention is not particularly limited, but it is preferably in the alkaline region because it is excellent in residue removing performance.
  • the pH of the treatment liquid is preferably 8 or more, more preferably 9 or more, still more preferably 10 or more, in that the anticorrosion performance against Co is more excellent.
  • the pH of the treatment liquid is preferably 14 or less, more preferably 12 or less, in that the anticorrosion performance against W is more excellent.
  • the treatment liquid may further contain a pH adjusting agent.
  • the treatment liquid of the present invention can be suitably used as a treatment liquid for semiconductor devices.
  • “for semiconductor devices” means that it is used in the manufacture of semiconductor devices.
  • the treatment liquid of the present invention can be used in any step for manufacturing a semiconductor device, for example, treatment of an insulating film, a resist or an antireflection film existing on a substrate, a dry etching residue (resist of a photoresist film and a residue of a photoresist film). It can be used for the treatment of metal hard mask residues, etc.) and the treatment of ashing residues.
  • the treatment liquid As a more specific use of the treatment liquid, it is applied on a substrate to improve the coatability of the composition before the step of forming a photoresist film using the sensitive light-sensitive or radiation-sensitive resin composition.
  • the treatment liquid of the present invention may be used for only one of the above-mentioned uses, or may be used for two or more uses.
  • the treatment liquid of the present invention is preferably used for treating a substrate having a metal layer containing at least one selected from the group consisting of W and Co.
  • the treatment liquid of the present invention is preferably used as a treatment liquid for producing a semiconductor device including a substrate having a metal layer containing at least one selected from the group consisting of W and Co.
  • the metal layer containing at least one selected from the group consisting of W and / or Co may be a metal layer containing only W and / or Co, and is an alloy containing W and / or Co. It may be a metal layer of another form containing W and / or Co.
  • the treatment liquid can be produced by a known method. Hereinafter, the method for producing the above-mentioned treatment liquid will be described in detail.
  • ⁇ Raw material refining process> In the production of the above-mentioned treatment liquid, it is desirable to purify any one or more of the raw materials for preparing the treatment liquid in advance by distillation, ion exchange, filtration or the like. As for the degree of purification, for example, it is preferable to purify the raw material to a purity of 99% or more, and more preferably to a purity of 99.9% or more.
  • the purification method is not particularly limited, and examples thereof include a method of passing through an ion exchange resin or an RO membrane (Reverse Osmosis Membrane), distillation, or a method such as filtering described later.
  • a purification device made of a cation exchange resin, an anion exchange resin, or a mixed bed type ion exchange resin to perform secondary purification.
  • Examples thereof include a method for carrying out purification.
  • the purification treatment may be carried out by combining a plurality of the above-mentioned known purification methods. Moreover, the purification treatment may be carried out a plurality of times.
  • the filter is not particularly limited as long as it has been conventionally used for filtration.
  • fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (high density).
  • PTFE polytetrafluoroethylene
  • PFA tetrafluoroethylene perfluoroalkyl vinyl ether copolymer
  • polyamide resins such as nylon
  • polyolefin resins such as polyethylene and polypropylene (PP) (high density).
  • PP polypropylene
  • a filter based on (including ultrahigh molecular weight) or the like can be mentioned.
  • a material selected from the group consisting of fluororesins such as polyethylene, polypropylene (including high-density polypropylene), PTFE and PFA, and polyamide-based resins such as nylon is preferable, and among them, fluororesins such as PTFE and PFA are preferable.
  • Resin filters are more preferred. By using a filter formed of these materials, it is possible to effectively remove highly polar foreign substances that are likely to cause defects.
  • the critical surface tension of the filter is preferably 70 mN / m or more, more preferably 95 mN / m or less, and even more preferably 75 to 85 mN / m.
  • the value of the critical surface tension is the nominal value of the manufacturer.
  • the pore diameter of the filter is preferably about 2 to 20 nm, more preferably 2 to 15 nm. Within this range, it is possible to reliably remove fine foreign substances such as impurities or agglomerates contained in the raw material while suppressing filtration clogging.
  • different filters may be combined. At that time, the filtering by the first filter may be performed only once or twice or more. When filtering is performed twice or more by combining different filters, it is preferable that the pore diameters of the second and subsequent times are the same or smaller than the pore diameter of the first filtering. Further, first filters having different pore diameters within the above-mentioned range may be combined.
  • the hole diameter here, the nominal value of the filter manufacturer can be referred to.
  • a commercially available filter for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd.
  • P-nylon filter (pore diameter 0.02 ⁇ m, critical surface tension 77 mN / m) made of polyamide; (manufactured by Nippon Pole Co., Ltd.), "PE clean filter (pore diameter 0.02 ⁇ m)” made of high-density polyethylene; (Manufactured by Nippon Pole Co., Ltd.) and "PE / Clean Filter (hole diameter 0.01 ⁇ m)” made of high-density polyethylene; (manufactured by Nippon Pole Co., Ltd.) can also be used.
  • the second filter a filter formed of the same material as the first filter described above can be used.
  • the pore size of the second filter is preferably about 1 to 10 nm.
  • the temperature at which the filtering step is performed is preferably room temperature (25 ° C.) or lower, more preferably 23 ° C. or lower, and even more preferably 20 ° C. or lower. Further, 0 ° C. or higher is preferable, 5 ° C. or higher is more preferable, and 10 ° C. or higher is further preferable.
  • particulate foreign matter or impurities can be removed, but at the above temperature, the amount of the particulate foreign matter and / or impurities dissolved in the raw material is reduced, so that filtering is more efficient. Will be removed.
  • the purification treatment may be carried out by adjusting to.
  • the preparation of the treatment liquid of the present invention is not particularly limited, and can be produced, for example, by mixing the above-mentioned components.
  • the order and / or timing of mixing each of the above-mentioned components is not particularly limited, and examples thereof include a method in which a hydroxyamine compound is dispersed in advance in pH-adjusted water and predetermined components are sequentially mixed.
  • the treatment liquid in the present invention may be a kit obtained by dividing the raw material into a plurality of parts.
  • a liquid composition in which a hydroxyamine compound and a basic compound are dispersed or dissolved in an organic solvent is prepared as the first liquid, and the first metal ion is prepared as the second liquid.
  • the treatment liquid may be prepared by using a concentrated liquid. When a concentrated solution of the treatment liquid is prepared, the concentration ratio thereof is appropriately determined depending on the composition of the composition, but is preferably 5 to 2000 times. That is, the treatment liquid may be used by diluting the concentrated liquid 5 to 2000 times.
  • the treatment liquid of the present invention can be filled in an arbitrary container, stored, transported, and used as long as corrosiveness or the like is not a problem (whether it is a kit or a concentrated liquid or not).
  • the container it is preferable that the container has a high degree of cleanliness and less elution of impurities for semiconductor applications.
  • usable containers include, but are not limited to, the "clean bottle” series manufactured by Aicello Chemical Corporation and the "pure bottle” manufactured by Kodama Resin Industry.
  • the inner wall of this container is made of one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a resin different from this, or stainless steel, hasteroi, inconel, monel, etc. It is preferably formed from a metal that has been subjected to rust and metal elution prevention treatment.
  • a fluororesin (perfluororesin) is preferable.
  • a container whose inner wall is a fluororesin by using a container whose inner wall is a fluororesin, a problem of elution of ethylene or propylene oligomer occurs as compared with a container whose inner wall is polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin. Can be suppressed.
  • Specific examples of such a container in which the inner wall is a fluororesin include a FluoroPure PFA composite drum manufactured by Entegris.
  • quartz and an electropolished metal material are also preferably used for the inner wall of the container.
  • the metal material used for producing the electropolished metal material includes at least one selected from the group consisting of chromium and nickel, and the total content of chromium and nickel is 25 with respect to the total mass of the metal material.
  • Metallic materials having a mass% of more than% are preferable, and examples thereof include stainless steel and nickel-chromium alloys.
  • the total content of chromium and nickel in the metal material is more preferably 30% by mass or more with respect to the total mass of the metal material.
  • the upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is generally preferably 90% by mass or less.
  • the stainless steel is not particularly limited, and known stainless steel can be used. Among them, an alloy containing 8% by mass or more of nickel is preferable, and an austenitic stainless steel containing 8% by mass or more of nickel is more preferable.
  • austenitic stainless steels include SUS (Steel Use Stainless) 304 (Ni content 8% by mass, Cr content 18% by mass), SUS304L (Ni content 9% by mass, Cr content 18% by mass), and SUS316 ( Ni content 10% by mass, Cr content 16% by mass), SUS316L (Ni content 12% by mass, Cr content 16% by mass) and the like.
  • the nickel-chromium alloy is not particularly limited, and a known nickel-chromium alloy can be used. Of these, nickel-chromium alloys having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass are preferable. Examples of the nickel-chromium alloy include Hastelloy (trade name, the same shall apply hereinafter), Monel (trade name, the same shall apply hereinafter), Inconel (trade name, the same shall apply hereinafter) and the like. More specifically, Hastelloy C-276 (Ni content 63% by mass, Cr content 16% by mass), Hastelloy-C (Ni content 60% by mass, Cr content 17% by mass), and Hastelloy C-22.
  • the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt and the like, if necessary, in addition to the above alloys.
  • the method for electropolishing a metal material is not particularly limited, and a known method can be used.
  • a known method can be used.
  • the methods described in paragraphs [0011]-[0014] of JP2015-227501 and paragraphs [0036]-[0042] of JP2008-264929 can be used.
  • the metal material is preferably buffed.
  • the method of buffing is not particularly limited, and a known method can be used.
  • the size of the abrasive grains used for finishing the buffing is not particularly limited, but # 400 or less is preferable because the unevenness on the surface of the metal material tends to be smaller.
  • the buffing is preferably performed before the electrolytic polishing.
  • the metal material may be processed by combining one or more of a plurality of stages of buffing, acid cleaning, magnetic fluid polishing, etc., which are performed by changing the count such as the size of abrasive grains. ..
  • a container having the container and the treatment liquid contained in the container may be referred to as a treatment liquid container.
  • the inside of these containers is cleaned before filling with the treatment liquid.
  • the liquid used for cleaning preferably has a reduced amount of metal impurities in the liquid.
  • the treatment liquid of the present invention may be bottling, transported and stored in a container such as a gallon bottle or a coated bottle after production.
  • the inside of the container may be replaced with an inert gas (chisso, argon, etc.) having a purity of 99.99995% by volume or more.
  • an inert gas chisso, argon, etc.
  • a gas having a low water content is preferable.
  • the temperature may be at room temperature, but in order to prevent deterioration, the temperature may be controlled in the range of ⁇ 20 ° C. to 20 ° C.
  • the clean room preferably meets the 14644-1 clean room standard. It is preferable to satisfy any one of ISO (International Organization for Standardization) class 1, ISO class 2, ISO class 3, and ISO class 4, more preferably ISO class 1 or ISO class 2, and ISO class 1 is satisfied. Is more preferable.
  • ISO International Organization for Standardization
  • the treatment liquid is used to clean a substrate having a metal layer containing one or more selected from the group consisting of W and Co.
  • An embodiment having a cleaning step (hereinafter, also referred to as “cleaning step B”) can be mentioned.
  • the cleaning method of the above aspect may include a treatment liquid preparation step (hereinafter referred to as "treatment liquid preparation step A") for preparing the treatment liquid before the cleaning step B.
  • treatment liquid preparation step A a treatment liquid preparation step for preparing the treatment liquid before the cleaning step B.
  • the object to be cleaned in the method for cleaning a substrate of the present invention is preferably a substrate having a metal layer containing at least one selected from the group consisting of W and Co.
  • the object to be cleaned in the method for cleaning the substrate of the present invention is, for example, a metal layer containing at least one selected from the group consisting of W and Co on the substrate (hereinafter, simply referred to as “metal layer”).
  • metal layer a metal layer containing at least one selected from the group consisting of W and Co on the substrate
  • Laminates provided with an interlayer insulating layer and a metal hard mask at least in this order. The laminate further has holes formed from the surface (opening) of the metal hard mask toward the substrate so as to expose the surface of the metal layer by undergoing a dry etching process or the like.
  • the method for producing a laminate having holes as described above is not particularly limited, but usually, for a pretreated laminate having a substrate, a metal layer, an interlayer insulating layer, and a metal hard mask in this order, A method of performing a dry etching process using a metal hard mask as a mask and etching the interlayer insulating layer so that the surface of the metal layer is exposed to provide holes penetrating the inside of the metal hard mask and the interlayer insulating layer. Can be mentioned.
  • the method for producing the metal hard mask is not particularly limited. For example, first, a metal layer containing a predetermined component is formed on the interlayer insulating layer, and a resist film having a predetermined pattern is formed on the metal layer.
  • the laminate may have a layer other than the above-mentioned layer, and examples thereof include an etching stop layer and an antireflection layer.
  • FIG. 1 shows a schematic cross-sectional view showing an example of a laminate that is a cleaning target of the substrate cleaning method of the present invention.
  • the laminate 10 shown in FIG. 1 is provided with a metal layer 2, an etching stop layer 3, an interlayer insulation layer 4, and a metal hard mask 5 in this order on a substrate 1, and is metal at a predetermined position after undergoing a dry etching process or the like.
  • a hole 6 is formed in which the layer 2 is exposed. That is, the object to be cleaned shown in FIG. 1 includes a substrate 1, a metal layer 2, an etching stop layer 3, an interlayer insulating layer 4, and a metal hard mask 5 in this order, and an opening of the metal hard mask 5.
  • the inner wall 11 of the hole 6 is composed of a cross-sectional wall 11a made of an etching stop layer 3, an interlayer insulating layer 4 and a metal hard mask 5, and a bottom wall 11b made of an exposed metal layer 2, to which a dry etching residue 12 adheres. doing.
  • the substrate cleaning method of the present invention can be suitably used for cleaning for the purpose of removing these dry etching residues 12. That is, while being excellent in removing the dry etching residue 12, it is also excellent in anticorrosion performance against the inner wall 11 (for example, the metal layer 2 and the like) of the object to be cleaned. Further, the method for cleaning the substrate of the present invention may be carried out on a laminate in which a dry ashing step is performed after the dry etching step.
  • a dry ashing step is performed after the dry etching step.
  • the metal hard mask preferably contains at least one component selected from the group consisting of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx.
  • Examples of the material of the metal hard mask include TiN, WO 2 and ZrO 2 .
  • the material of the interlayer insulating layer is not particularly limited, and a material having a dielectric constant k of 3.0 or less is preferable, and a material having a dielectric constant k of 2.6 or less is more preferable.
  • Specific examples of the material of the interlayer insulating layer include SiO 2 , SiOC materials, and organic polymers such as polyimide.
  • the material of the etching stop layer is not particularly limited. Specific examples of the etching stop layer material include SiN, SiON, SiOCN-based materials, and metal oxides such as AlOx.
  • the wiring material forming the metal layer contains at least W (tungsten) or Co (cobalt). Further, these metals may be alloys with other metals.
  • the wiring material of the present invention may further contain a metal other than W and Co, a metal nitride or an alloy. Specific examples thereof include copper, titanium, titanium-tungsten, titanium nitride, tantalum, tantalum compounds, chromium, chromium oxide, and aluminum.
  • the "substrate” here includes, for example, a semiconductor substrate made of a single layer and a semiconductor substrate made of multiple layers.
  • the material constituting the semiconductor substrate composed of a single layer is not particularly limited, and is generally preferably composed of a Group III-V compound such as silicon, silicon germanium, or GaAs, or any combination thereof.
  • the configuration is not particularly limited, and for example, an interconnect structure (interconnect features) such as a metal wire and a dielectric material is exposed and integrated on the above-mentioned semiconductor substrate such as silicon. It may have a circuit structure.
  • Metals and alloys used in interconnect structures include, but are limited to, aluminum, aluminum alloyed with copper, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. It's not a thing. Further, a layer such as an interlayer dielectric layer, silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide may be provided on the semiconductor substrate.
  • the treatment liquid preparation step A is a step of preparing the treatment liquid.
  • Each component used in this step is as described above.
  • the procedure of this step is not particularly limited, and for example, a hydroxyamine compound, a basic compound, an organic solvent, a first metal ion, and other optional components are added and mixed by stirring to prepare a treatment liquid.
  • the method of preparation is mentioned.
  • each component When each component is added, it may be added all at once, or it may be added in multiple portions.
  • one classified as a semiconductor grade or one classified as a high-purity grade equivalent thereto is used to remove foreign substances by filtering and / or reduce ion components by ion exchange resin or the like.
  • the raw material components excluding the first metal ion contain a metal ion corresponding to the first metal ion and the total content thereof exceeds a predetermined amount
  • the hydroxyamine compound and the basic compound After mixing the organic solvent and other optional components as necessary, by removing foreign substances by filtering and / or reducing the ionic components by an ion exchange resin or the like, a predetermined amount of the first metal ion, the hydroxyamine compound, and A treatment liquid containing a basic compound, an organic solvent, and if necessary, other optional components may be prepared.
  • the concentrated solution is diluted to obtain a diluted solution before performing the cleaning step B, and then the cleaning step B is performed using this diluted solution. ..
  • the above dilution is preferably carried out using a diluent containing water.
  • the method of bringing the treatment liquid into contact with the cleaning target is not particularly limited, and for example, a method of immersing the cleaning target in the treatment liquid placed in the tank, a method of spraying the treatment liquid on the cleaning target, and a method of spraying the treatment liquid on the cleaning target.
  • a method of flowing the treatment liquid into the water, or any combination thereof can be mentioned. From the viewpoint of residue removing performance, a method of immersing the object to be cleaned in the treatment liquid is preferable.
  • the temperature of the treatment liquid is preferably 90 ° C. or lower, more preferably 25 to 80 ° C., further preferably 30 to 75 ° C., and particularly preferably 40 to 70 ° C.
  • the cleaning time can be adjusted according to the cleaning method used and the temperature of the treatment liquid.
  • the cleaning time is preferably 60 minutes or less, more preferably 1 to 60 minutes, and 3 to 20 minutes. Minutes are more preferred, and 4 to 15 minutes are particularly preferred.
  • the washing time is preferably 10 seconds to 5 minutes, more preferably 15 seconds to 4 minutes, further preferably 15 seconds to 3 minutes, and particularly preferably 20 seconds to 2 minutes.
  • a mechanical stirring method may be used in order to further improve the cleaning ability of the treatment liquid.
  • the mechanical stirring method include a method of circulating the treatment liquid on the object to be cleaned, a method of flowing or spraying the treatment liquid on the object to be cleaned, and a method of stirring the treatment liquid by ultrasonic waves or megasonic. And so on.
  • the method for cleaning a substrate using the treatment liquid of the present invention may further include a step of rinsing and cleaning the object to be cleaned with a solvent (hereinafter referred to as "rinsing step B2") after the cleaning step B. ..
  • the rinsing step B2 is preferably performed continuously with the washing step B and is a step of rinsing with a rinsing solvent (rinsing solution) for 5 seconds to 5 minutes.
  • the rinsing step B2 may be performed by using the above-mentioned mechanical stirring method.
  • rinsing solvent examples include deionized (DI: De Ionize) water, methanol, ethanol, isopropyl alcohol, N-methylpyrrolidinone, ⁇ -butyrolactone, dimethyl sulfoxide, ethyl lactate and propylene glycol monomethyl ether acetate. It is not limited to. Alternatively, an aqueous rinse solution having a pH> 8 (diluted aqueous ammonium hydroxide, etc.) may be used.
  • DI De Ionize
  • ammonium hydroxide aqueous solution, DI water, methanol, ethanol, or isopropyl alcohol is preferable, ammonium hydroxide aqueous solution, DI water, or isopropyl alcohol is more preferable, and ammonium hydroxide aqueous solution or DI water is further preferable.
  • a method of bringing the rinse solvent into contact with the object to be cleaned the above-mentioned method of bringing the treatment liquid into contact with the object to be cleaned can be similarly applied.
  • the temperature of the rinsing solvent in the rinsing step B2 is preferably 16 to 27 ° C.
  • the method for cleaning a substrate using the treatment liquid of the present invention may include a drying step B3 for drying the object to be cleaned after the rinsing step B2.
  • the drying method is not particularly limited. Examples of the drying method include a spin drying method, a method of flowing a dry gas over an object to be cleaned, a method of heating a substrate by a heating means such as a hot plate or an infrared lamp, a flatulence drying method, a rotagoni drying method, and an IPA. (Isopropyl alcohol) drying method, or any combination thereof can be mentioned.
  • the drying time depends on the specific method used, but is generally preferably 30 seconds to several minutes.
  • the objects to be cleaned in the method for cleaning a substrate using the treatment liquid of the present invention are a metal layer, an interlayer insulating layer, and a metal hard including one or more selected from the group consisting of W and Co on the substrate as described above. It is not limited to a laminate having masks at least in this order. That is, for example, it is also used for removing a photoresist etching residue of a laminate having a metal layer containing at least one selected from the group consisting of W and Co, an interlayer insulating layer, and a photoresist film on the substrate in this order. it can.
  • treatment solution 1 The treatment solutions (treatment solutions 1 to 8) shown in Table 1 were prepared respectively. The contents of various components used in each treatment liquid (all based on mass) are as described in the table.
  • a mixed solution was prepared by mixing each component so as to have the formulation shown in Table 1.
  • the first metal ion and the second metal ion were introduced into the liquid by adding a metal salt (metal chloride) containing the corresponding metal atom.
  • the content of metal ions in the treatment liquid was measured by the method described above. Those below the detection limit were measured after appropriately concentrating the drug solution, and the converted value was used.
  • HA Hydroxylamine
  • HAS Hydroxylamine Sulfate
  • DTPA Diethylenetriamine pentaacetic acid
  • EGBE Ethylene glycol monobutyl ether
  • 5M-BTA 5-Methyl-1H-benzotriazole
  • DBU Diazabicycloundecene
  • the substrate on which the Co film was formed was immersed in the treatment solution (65 ° C.) after the thermocycle treatment for 5 minutes, and the difference in the film thickness of the Co film before and after immersion in the treatment solution showed that the treatment solution
  • the etching rate ( ⁇ / min) for the Co film was calculated, and the etching rate was defined as ER Age .
  • the stability of anticorrosion performance against Co film over time was evaluated. The closer the etching rate maintenance rate (%) is to 100%, the better the maintenance rate of the anticorrosion performance against the Co film. That is, the anticorrosion performance against the Co film is stable over time.
  • the etching rate maintenance rate (%) was evaluated based on the following evaluation criteria.
  • Etching rate maintenance rate (%) is 100 to 102%
  • AA Etching rate maintenance rate (%) is more than 102% and 106% or less
  • a + Etching rate maintenance rate (%) is more than 106% and 114% or less
  • A- Etching rate maintenance rate (%) is 114 % More than 130%
  • B Etching rate maintenance rate (%) is more than 130% and less than 200%
  • C Etching rate maintenance rate (%) is more than 200% and less than 430%
  • D Etching rate maintenance rate ( %) Is over 430%
  • the etching rate maintenance rate (%) is preferably 100 to 114%, more preferably 100 to 106%, and even more preferably 100 to 102%.
  • the substrate provided with the TiO 2 film is immersed in the treatment liquid (65 ° C.) after the thermocycle treatment for 5 minutes, and the treatment is performed based on the difference in the thickness of the dio 2 film before and after the immersion in the treatment liquid.
  • the etching rate ( ⁇ / min) of the liquid with respect to the TiO 2 film was calculated, and the etching rate was defined as ER Age .
  • the stability of the residue removability over time was evaluated. The closer the etching rate maintenance rate (%) is to 100%, the better the maintenance rate of the residue removal performance. That is, the residue-removing property with time is good.
  • the etching rate maintenance rate (%) was evaluated based on the following evaluation criteria.
  • the etching rate retention rate (%) is preferably 86 to 100%, more preferably 92 to 100%, and even more preferably 97 to 100%.
  • Table 1 shows the basic compositions of the treatment liquids 1 to 8.
  • Tables 2 (No. 1) to (No. 4) show the composition and content of the first metal ion and the second metal ion in the treatment liquid 1 in Table 1, and the evaluation result of the treatment liquid 1. That is, for example, the treatment liquid of Example 1001 shown in Table 2 (No. 1) is the treatment liquid 1 shown in Table 1, and Na, Al, K, Ca, Cr, Fe, Ni, as the first metal ion.
  • All metal ions selected from the group consisting of and Zn are contained in a total content of 400.0 mass ppb with respect to the total mass of the treatment liquid, and Li, Mg, Mn, Cu, Ag, as second metal ions. It is a treatment liquid containing 5.55 mass ppb in total content with respect to the total mass of the treatment liquid, which contains all the metal ions selected from the group consisting of Pb and Co.
  • Tables 3 (No. 1) to (No. 3) show the composition and content of the first metal ion in the treatment liquid 2 in Table 1, and the evaluation results of the treatment liquid 2.
  • the treatment liquid 2 does not contain the second metal ion (below the detection limit).
  • Tables 5 (No. 1) to (No. 3) show the composition and content of the first metal ion in the treatment liquid 4 in Table 1, and the evaluation results of the treatment liquid 4.
  • the treatment liquid 4 does not contain the second metal ion (below the detection limit).
  • Tables 6 (No. 1) to (No. 3) show the composition and content of the first metal ion in the treatment liquid 5 in Table 1, and the evaluation results of the treatment liquid 5.
  • the treatment liquid 5 does not contain the second metal ion (below the detection limit).
  • Tables 8 (No. 1) to (No. 3) show the composition and content of the first metal ion in the treatment liquid 7 in Table 1, and the evaluation results of the treatment liquid 7.
  • the treatment liquid 7 does not contain the second metal ion (below the detection limit).
  • Tables 9 (No. 1) to (No. 3) show the composition and content of the first metal ion in the treatment liquid 8 in Table 1, and the evaluation results of the treatment liquid 8.
  • the treatment liquid 8 does not contain the second metal ion (below the detection limit).
  • the treatment liquid when the treatment liquid satisfies the requirements X1 and Y1 (corresponding to Examples 1001A to 1017A and Examples 1001B to 1017B), more preferably when the treatment liquid satisfies the requirements X1 and the requirement Y2 (Examples 1001 to 1017). It is clear that it is superior in performance stability of residue removal performance and anticorrosion performance.
  • the treatment liquid contains two or more first metal ions, and the content of each metal ion is 1.0 mass ppb to 100.0 mass ppb with respect to the total mass of the treatment liquid. is there.
  • the treatment liquid contains a second metal ion.
  • the treatment liquid contains two or more kinds of second metal ions, and the total content thereof is 0.01 mass ppb to 10.0 mass ppb with respect to the total mass of the treatment liquid, and further, the treatment liquid.
  • the content of each second metal ion contained therein is 0.01 mass ppb to 1.0 mass ppb with respect to the total mass of the treatment liquid.
  • the treatment liquid of the comparative example cannot achieve both the residue removal performance and the anticorrosion performance stability when the temperature environment changes such as refrigerated storage and room temperature standing are repeated.

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Abstract

La présente invention vise à fournir un liquide de traitement qui conserve une excellente performance d'élimination de résidus et une excellente performance de prévention de la corrosion, même lorsqu'il est soumis à plusieurs reprises à des changements d'environnement thermique entre un stockage à froid et un stockage à température ambiante.　Ce liquide de traitement comprend un composé d'hydroxyamine sélectionné dans le groupe constitué d'hydroxyamines et de sels d'hydroxyamine, un solvant organique, un composé basique, et au moins un type de premier ion métallique sélectionné dans le groupe constitué des Na, Al, K, Ca, Cr, Fe, Ni, et Zn. La teneur totale en le premier ion métallique du liquide de traitement est de 7,0 à 800,0 ppb en masse par rapport à la masse totale du liquide de traitement.
PCT/JP2020/031798 2019-08-29 2020-08-24 Liquide de traitement WO2021039701A1 (fr)

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Citations (5)

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WO2017208767A1 (fr) * 2016-06-03 2017-12-07 富士フイルム株式会社 Liquide de traitement, procédé de nettoyage de substrat et procédé d'élimination de résine photosensible
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