WO2017119334A1 - Liquide de traitement, procédé de nettoyage de substrat et procédé de fabrication de dispositif à semi-conducteur - Google Patents

Liquide de traitement, procédé de nettoyage de substrat et procédé de fabrication de dispositif à semi-conducteur Download PDF

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Publication number
WO2017119334A1
WO2017119334A1 PCT/JP2016/088670 JP2016088670W WO2017119334A1 WO 2017119334 A1 WO2017119334 A1 WO 2017119334A1 JP 2016088670 W JP2016088670 W JP 2016088670W WO 2017119334 A1 WO2017119334 A1 WO 2017119334A1
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Prior art keywords
treatment liquid
cleaning
compound
substrate
liquid
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PCT/JP2016/088670
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English (en)
Japanese (ja)
Inventor
朗子 吉井
祐継 室
智美 高橋
清水 哲也
智威 高橋
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富士フイルム株式会社
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Priority to KR1020187018802A priority Critical patent/KR102027793B1/ko
Priority to JP2017560115A priority patent/JP6542393B2/ja
Publication of WO2017119334A1 publication Critical patent/WO2017119334A1/fr

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02Inorganic compounds
    • C11D7/04Water-soluble compounds
    • C11D7/10Salts
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/32Organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/34Organic compounds containing sulfur
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041Cleaning
    • H01L21/02043Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02052Wet cleaning only
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041Cleaning
    • H01L21/02079Cleaning for reclaiming
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302Treatment 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
    • H01L21/304Mechanical treatment, e.g. grinding, polishing, cutting
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/14Hard surfaces
    • C11D2111/22Electronic devices, e.g. PCBs or semiconductors

Definitions

  • Patent Document 1 discloses that a composition containing water, a hydroxylamine salt compound, and a corrosion inhibitor is used as the treatment liquid (claim 1 and the like).
  • Cleaning step D for cleaning A drainage recovery step E for recovering the drainage used in the cleaning step D; Further comprising The substrate cleaning method according to [9], wherein the cleaning step D and the drainage recovery step E are repeatedly performed to recycle the drainage.
  • the triazole compound examples include a triazole compound having a benzene ring structure (that is, a benzotriazole compound), a triazole compound having no benzene ring structure, and the like.
  • the treatment liquid preferably contains at least one compound selected from benzotriazole, carboxybenzotriazole, 5-methyl-benzotriazole, and triazole from the viewpoint of further improving the anticorrosion performance, and 5-methyl- More preferably, it contains benzotriazole.
  • the number of objects having a size of 0.05 ⁇ m or more contained in the treatment liquid of the present invention is 1 to 2000, preferably 1 to 1000, and more preferably 1 to 400.
  • the number is more preferably 1 or more and less than 300, and particularly preferably 1 to 100.
  • the residue removal performance and anticorrosion performance of the treatment liquid are excellent, and the residue removal performance and corrosion prevention performance of the treatment liquid after repeated environmental temperature changes are excellent. It will be a thing.
  • the residue removal performance and the anticorrosion performance of the treatment liquid are insufficient, or the anticorrosion performance of the treatment liquid after repeated environmental temperature changes is insufficient. It becomes.
  • the number of the objects to be counted is more than 2000, the anticorrosion performance of the treatment liquid becomes insufficient, or the residue removal performance and anticorrosion performance of the treatment liquid after repeated environmental temperature changes are insufficient. It becomes.
  • DTPA diethylenetriaminepentaacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • trans-1,2-diaminocyclohexanetetraacetic acid are preferable. These compounds can be blended alone or in combination of two or more.
  • water-soluble alcohol examples include alkane diol (for example, including alkylene glycol), alkoxy alcohol (for example, including glycol monoether), saturated aliphatic monohydric alcohol, unsaturated non-aromatic monohydric alcohol, and ring.
  • alkane diol for example, including alkylene glycol
  • alkoxy alcohol for example, including glycol monoether
  • saturated aliphatic monohydric alcohol unsaturated non-aromatic monohydric alcohol
  • ring A low molecular weight alcohol containing a structure is mentioned.
  • alkoxy alcohol examples include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, and water-soluble 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.
  • water-soluble ketones include acetone, propanone, cyclobutanone, cyclopentanone, cyclohexanone, diacetone alcohol, 2-butanone, 5-hexanedione, 1,4-cyclohexanedione, 3-hydroxyacetophenone, 1,3-cyclohexane.
  • Examples include dione and cyclohexanone.
  • Water-soluble esters 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, ethylene glycol Examples include glycol monoether monoesters such as monoethyl ether acetate. Among these, ethylene glycol monobutyl ether, tri (propylene glycol) methyl ether, and diethylene glycol monoethyl ether are preferable.
  • water-soluble organic solvents water-soluble alcohols are preferable, alkanediols, glycols, and alkoxy alcohols are more preferable, and alkoxy alcohols are particularly preferable from the viewpoint of further improving the corrosion prevention effect.
  • the water-soluble organic solvents may be used alone or in combination of two or more.
  • the pH of the treatment liquid of the present invention is not particularly limited, but is preferably not less than pKa of hydroxylamine and a conjugate acid of hydroxylamine salt. Residue removal performance is dramatically improved by being pKa or more of the conjugate acid of hydroxylamine and hydroxylamine salt. In other words, when the ratio of hydroxylamine and hydroxylamine salt present in the molecular state in the treatment liquid is large, the effect of the present invention is remarkably obtained. For example, the pKa of hydroxylamine conjugate acid is about 6.
  • the treatment liquid of the present invention is preferably adjusted to pH 3-11. In order to bring the pH of the treatment liquid into the above range, it is desirable that the treatment liquid contains a pH adjusting agent. When the pH of the treatment liquid is within the above range, both the corrosion rate and the residue removal performance are more excellent. As a measuring method of pH, it can measure using a well-known pH meter.
  • the treatment liquid of the present invention may contain quaternary ammonium hydroxides.
  • residue removal performance can be further improved, and it can also function as a pH adjuster.
  • the quaternary ammonium hydroxide is preferably a compound represented by the following general formula (4).
  • R 4A to R 4D each independently represent an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, butyl group, etc.), or a hydroxyalkyl group having 1 to 6 carbon atoms (for example, A hydroxymethyl group, a hydroxyethyl group, a hydroxybutyl group, etc.), a benzyl group, or an aryl group (for example, a phenyl group, a naphthyl group, a naphthalene group, etc.). Of these, an alkyl group, a hydroxyethyl group, and a benzyl group are preferable.
  • tetramethylammonium hydroxide tetraethylammonium hydroxide
  • benzyltrimethylammonium hydroxide choline
  • Quaternary ammonium hydroxides may be used alone or in combination of two or more.
  • the content of the quaternary ammonium hydroxide in the treatment liquid is preferably 0.1 to 15% by mass, and preferably 0.5 to 10% by mass with respect to the total mass of the treatment liquid of the present invention. Is more preferably 0.5 to 5% by mass.
  • alkanolamines In the treatment liquid, solubilization of additive components and organic residue may be promoted, and alkanolamines may be contained from the viewpoint of preventing corrosion.
  • the alkanolamines may be any of primary amines, secondary amines, and tertiary amines, and are preferably monoamines, diamines, or triamines, and more preferably monoamines.
  • the alkanol group of the amine preferably has 1 to 5 carbon atoms.
  • a compound represented by the following formula (5) is preferable.
  • alkanolamines include monoethanolamine, diethanolamine, triethanolamine, tert-butyldiethanolamine, isopropanolamine, 2-amino-1-propanol, 3-amino-1-propanol, isobutanolamine, 2 -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 of alkanolamines in the treatment liquid is preferably 0.1 to 80% by mass, more preferably 0.5 to 50% by mass, based on the total mass of the treatment liquid of the present invention. More preferably, the content is 0.5 to 20% by mass.
  • the treatment liquid of the present invention may contain other additives as long as the effects of the present invention are achieved.
  • other additives include surfactants and antifoaming agents.
  • the treatment liquid in the present invention can be stored, transported and used in any container as long as corrosivity is not a problem (regardless of whether it is a kit or not).
  • 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 or its container is subjected to a resin different from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a rust prevention / metal elution prevention treatment.
  • a resin different from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a rust prevention / metal elution prevention treatment.
  • a fluorine-based resin perfluoro resin
  • the processing liquid of the present invention is not particularly limited with respect to its production method. It can manufacture by fully mixing a predetermined raw material using stirrers, such as a mixing mixer. Moreover, the method of mixing after preparing to preset pH previously, or the method of adjusting to preset pH after mixing can be used. Furthermore, it is also possible to use a method in which a concentrated solution containing the above compound is produced and diluted to a predetermined concentration at the time of use. Moreover, it can also be used by adjusting the concentrated solution to a set pH after dilution. A predetermined amount of pure water for dilution can be added to the concentrate, and a predetermined amount of concentrate can be added to the pure water for dilution.
  • the treatment liquid of the present invention is for mixing a predetermined raw material and then counting the number of objects to be counted having a size of 0.05 ⁇ m or more, which is counted by a light scattering type liquid particle counter, per ml. It is preferable to have a process.
  • examples of the object to be cleaned in the substrate cleaning method of the present invention include a laminate including a metal film, an interlayer insulating film, and a metal hard mask on the substrate at least in this order.
  • the laminate further has a hole formed from the surface (opening) of the metal hard mask toward the substrate so as to expose the metal film surface through a dry etching process or the like.
  • the manufacturing method of the laminate having holes as described above is not particularly limited, but is usually a pre-treatment laminate having a substrate, a metal film, an interlayer insulating film, and a metal hard mask in this order.
  • FIG. 1 the cross-sectional schematic diagram which shows an example of the laminated body which is the washing
  • a laminate 10 shown in FIG. 1 includes a metal film 2, an etching stopper layer 3, an interlayer insulating film 4, and a metal hard mask 5 in this order on a substrate 1, and a metal film at a predetermined position after a dry etching process or the like.
  • a hole 6 through which 2 is exposed is formed. That is, the object to be cleaned shown in FIG. 1 includes a substrate 1, a metal film 2, an etching stop layer 3, an interlayer insulating film 4, and a metal hard mask 5 in this order, and an opening of the metal hard mask 5.
  • the wiring material for forming the metal film is not particularly limited, and examples thereof include metals, metal nitrides, and alloys. Specific examples include copper, titanium, titanium-tungsten, titanium nitride, tungsten, cobalt, tantalum, tantalum compounds, chromium, chromium oxide, and aluminum. From the viewpoint of enjoying the effect of the treatment liquid of the present invention, cobalt and tungsten are particularly desirable as the wiring material.
  • the component having a large amount of impurities at the time of the raw material it is preferable to use a component that has been subjected to foreign substance removal by filtering and ion component reduction by an ion exchange resin or the like. Furthermore, it is preferable to perform the above-described processing such as filtering so that the number of the objects to be counted included in the processing liquid falls within a desired range.
  • the substrate cleaning method of the present invention may further include, after the cleaning step B, a step of rinsing the substrate with a mask with a solvent (rinsing step B2).
  • the rinsing step B2 is preferably performed continuously with the cleaning step B and is a rinsing step with a rinsing solvent for 5 seconds to 5 minutes.
  • the rinsing step B2 may be performed using the mechanical stirring method described above.
  • the rinsing solvent ammonium hydroxide aqueous solution, DI water, methanol, ethanol and isopropyl alcohol are preferable, ammonium hydroxide aqueous solution, DI water and isopropyl alcohol are more preferable, and ammonium hydroxide aqueous solution and DI water are preferable. Further preferred.
  • a method for bringing the rinsing solvent into contact with the substrate with mask the above-described method for bringing the treatment liquid into contact with the substrate with mask can be similarly applied.
  • the temperature of the rinsing solvent in the rinsing step B2 is preferably 16 to 27 ° C. You may use the process liquid mentioned above as a rinse solvent of rinse process B2.
  • a cleaning step D for cleaning a substrate comprising: A drainage recovery step E for recovering the drainage of the processing liquid used in the cleaning step D, and The washing step D and the drainage recovery step E are repeatedly performed.
  • the cleaning process D for cleaning the substrate using the collected drainage of the processing liquid is synonymous with the cleaning process B in the above-described aspect, and the preferable aspect is also the same.
  • the drainage recovery means in the drainage recovery steps C and E is not particularly limited.
  • the collected waste liquid is preferably stored in the above-described resin container in the above-described static elimination process J, and at this time, a static elimination process similar to that in the static elimination process J may be performed.
  • HA Hydroxylamine (BASF)
  • HAS hydroxylammonium sulfate (manufactured by BASF)
  • HAC hydroxylammonium hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.)
  • HAN hydroxylammonium nitrate (manufactured by Sigma-Aldrich)
  • the etching solutions of the TiO 2 film were performed using the respective treatment liquids of Examples and Comparative Examples within 24 hours after preparation. Specifically, by immersing the TiO 2 film 5 minutes in the treatment liquid of the examples and comparative examples, on the basis of the thickness difference of the TiO 2 film before and after immersion in the processing solution, the etching rate ( ⁇ / min) Calculated.
  • the film thickness of the TiO 2 film before and after the treatment was measured using an ellipsometry (spectral ellipsometer, trade name “Vase”, manufactured by JA Woollam Japan Co., Ltd.) with a measurement range of 250 to 1000 nm and a measurement angle of 70.
  • etching rate (ER) of the TiO 2 film was evaluated according to the following evaluation criteria.
  • thermocycle test Evaluation of residue removal performance after thermocycle test
  • Each treatment solution was sealed in a container (clean bottle made by Aicello Chemical).
  • one cycle is to leave the container filled with the treatment liquid under the condition of 12 hours at 5 ° C., and then leave the container filled with the treatment liquid under the condition of 12 hours at 30 ° C.
  • a thermocycle test was repeated 90 times.
  • the thermocycle test in the Example column is a test corresponding to repeated temperature environment changes.
  • an evaluation test of the residue removal performance was performed in the same procedure as the above "(a) Evaluation of residue removal performance within 24 hours after preparation”.
  • the evaluation criteria are the same as in the above “(a) Evaluation of residue removal performance within 24 hours after preparation”.
  • the concentration of Fe ions contained in the treatment liquid is within the range of 10 mass ppt to 1000 mass ppb (Examples 17, 18, 21, and 22)
  • the residue removal performance after long-term refrigerated storage is excellent. Indicated.
  • the Fe ion concentration contained in the treatment liquid is in the range of 10 mass ppt or more and less than 1000 mass ppt (Examples 17 and 21)
  • the content ratio (mass ratio) of the mercapto group-containing compound to the triazole compound contained as a corrosion inhibitor in the treatment liquid is 0.1. It was shown that the residue removal performance and anticorrosion performance after long-term refrigerated storage were further improved by being in the range of ⁇ 50 (Examples 26, 27, and 28). Further, it was shown that the residue removal performance and anticorrosion performance after long-term refrigerated storage were further improved when the content ratio was in the range of 0.1 to 20 (Examples 26 and 27). Furthermore, it was shown that when the content ratio is in the range of 0.1 to 10 (Example 26), the residue removal performance and anticorrosion performance after long-term refrigeration storage are further improved.
  • the residue removal performance did not change for each of the treatment liquids when it passed through the above-described charge removal step and when it did not.
  • the anticorrosion performance of the Co film, the anticorrosion performance of the W film, and the anticorrosion performance of the SiOx film the anticorrosion performance is better when the neutralization process is performed than when the neutralization process is not performed. Obtained. From this result, it was found that the anti-corrosion performance of the treatment liquid was more excellent by passing through the static elimination step.
  • the treatment liquid of Example 20 when the recycle test was performed, the residue removal performance and the anticorrosion performance of the Co film and the W film were “B”, which was the same as the case where the recycle test was not performed. Results were obtained. From these results, it has been found that the treatment liquid of the present invention can suppress a decrease in performance and is excellent in recyclability even when a substrate is repeatedly treated.

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Abstract

Un objet de la présente invention est de fournir un liquide de traitement qui présente une excellente performance d'élimination de résidus et une excellente performance anti-corrosion, et qui présente encore une excellente performance d'élimination de résidus et une excellente performance anti-corrosion même après plusieurs changements de température. Un autre objet de la présente invention est de fournir un procédé de nettoyage d'un substrat et un procédé de fabrication d'un dispositif à semi-conducteur. Un liquide de traitement selon l'invention est un liquide de traitement pour dispositifs à semi-conducteur, qui contient de l'eau, un inhibiteur de corrosion et au moins un composé d'hydroxylamine qui est choisi parmi l'hydroxylamine et des sels d'hydroxylamine, le nombre de corps comptés ayant une dimension supérieure ou égale à 0,05 µm étant de 1 à 2 000 pour 1 ml du liquide de traitement, compté par un compteur de particules liquidien de type à diffusion de lumière.
PCT/JP2016/088670 2016-01-05 2016-12-26 Liquide de traitement, procédé de nettoyage de substrat et procédé de fabrication de dispositif à semi-conducteur WO2017119334A1 (fr)

Priority Applications (2)

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KR1020187018802A KR102027793B1 (ko) 2016-01-05 2016-12-26 처리액, 기판의 세정 방법 및 반도체 디바이스의 제조 방법
JP2017560115A JP6542393B2 (ja) 2016-01-05 2016-12-26 処理液、基板の洗浄方法および半導体デバイスの製造方法

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JP2016000727 2016-01-05
JP2016-000727 2016-01-05

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
JPWO2017119244A1 (ja) * 2016-01-05 2018-10-25 富士フイルム株式会社 処理液、基板の洗浄方法、および、半導体デバイスの製造方法
WO2019021741A1 (fr) * 2017-07-28 2019-01-31 株式会社Screenホールディングス Procédé de neutralisation de liquide de traitement, procédé de traitement de substrat, et système de traitement de substrat
JP2021034549A (ja) * 2019-08-23 2021-03-01 東京応化工業株式会社 充填剤、基板の処理方法、及び充填剤の製造方法
WO2022176663A1 (fr) * 2021-02-22 2022-08-25 富士フイルム株式会社 Liquide de nettoyage et procédé de nettoyage d'un substrat semi-conducteur
JP7288511B2 (ja) 2019-08-23 2023-06-07 富士フイルム株式会社 洗浄剤組成物

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WO2022176663A1 (fr) * 2021-02-22 2022-08-25 富士フイルム株式会社 Liquide de nettoyage et procédé de nettoyage d'un substrat semi-conducteur

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