WO2015083636A1 - Liquide nettoyant, procédé de nettoyage d'un substrat semi-conducteur, et procédé de formation d'un motif métallique - Google Patents

Liquide nettoyant, procédé de nettoyage d'un substrat semi-conducteur, et procédé de formation d'un motif métallique Download PDF

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Publication number
WO2015083636A1
WO2015083636A1 PCT/JP2014/081545 JP2014081545W WO2015083636A1 WO 2015083636 A1 WO2015083636 A1 WO 2015083636A1 JP 2014081545 W JP2014081545 W JP 2014081545W WO 2015083636 A1 WO2015083636 A1 WO 2015083636A1
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Prior art keywords
cleaning liquid
cleaning
carbon atoms
ammonium hydroxide
group
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PCT/JP2014/081545
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English (en)
Japanese (ja)
Inventor
至郎 森田
真吾 成瀬
和彦 香村
考一 藤原
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Jsr株式会社
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Publication of WO2015083636A1 publication Critical patent/WO2015083636A1/fr

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Classifications

    • 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
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • 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
    • C11D7/06—Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • 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
    • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5013—Organic solvents containing nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • 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
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

Definitions

  • the present invention relates to a cleaning liquid and a method for cleaning a semiconductor substrate.
  • An object of the present invention is to provide a cleaning solution that is excellent in decomposability of organic substances and has little corrosion on metals in a cleaning solution that does not substantially contain water, and a method for cleaning a semiconductor substrate using the cleaning solution. With the goal.
  • the present invention includes the following [1] to [6].
  • [1] A cleaning liquid substantially free of water, Containing 2 to 10% by mass of a quaternary ammonium hydroxide, glycols, and an amide organic solvent, A cleaning liquid, wherein the content (mass) of the glycol is at least 5 times the content (mass) of the quaternary ammonium hydroxide.
  • [2] The cleaning liquid according to [1], wherein the content (mass) of the glycol is 5 to 20 times the content (mass) of the quaternary ammonium hydroxide.
  • [3] The cleaning liquid according to [1] or [2], wherein the amide organic solvent is at least one selected from a compound represented by the following formula (1) and a compound represented by the following formula (2).
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 4 to 10 carbon atoms.
  • X represents a methylene group or a divalent group represented by —NR 2 —.
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 3.
  • R 3 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group in which a hydrogen atom of an alkyl group having 1 to 6 carbon atoms is substituted with an alkoxy group having 1 to 6 carbon atoms.
  • the cleaning agent of the present invention does not substantially contain water, has excellent organic decomposability, and has little corrosion on metals.
  • the semiconductor substrate cleaning method using this cleaning liquid can satisfactorily remove organic substances without corroding metals such as copper and aluminum on the substrate to be processed.
  • the cleaning liquid of the present invention is a cleaning liquid substantially free of water, Containing 2 to 10% by mass of a quaternary ammonium hydroxide, glycols, and an amide organic solvent,
  • the glycol content (mass) is 5 times or more the content (mass) of the quaternary ammonium hydroxide.
  • the cleaning solution In order to increase the number of times the cleaning solution is used, it is necessary to decompose organic substances such as resist film residues as finely as possible.
  • the cleaning solution must contain 2 to 10% by mass of a quaternary ammonium hydroxide that is a strong base. There is.
  • the quaternary ammonium hydroxide has a problem that it corrodes metals such as copper and aluminum on the substrate to be processed.
  • the present inventor has 2 to 10% by mass of quaternary ammonium hydroxide and glycols at least 5 times the quaternary ammonium hydroxide content (mass). It has been found that the cleaning solution contained is excellent in the decomposability of organic substances and has little corrosion on metals.
  • Quaternary ammonium hydroxide Quaternary ammonium hydroxide has a very high degree of ionization and generates hydroxide ions that are quantitatively strong bases. Hydroxide ions have a strong ability to decompose organic substances, and also have a strong ability to react with fine particles such as silica and promote the solubility of fine particles. Thus, since the quaternary ammonium hydroxide is excellent in the decomposability
  • the quaternary ammonium hydroxide includes tetramethylammonium hydroxide, tetraethylammonium hydroxide, 1,1-dimethylaziridinium hydroxide, tetrabutylammonium hydroxide, dimethyldipropylammonium hydroxide, diethyldipropylammonium hydroxide.
  • Alkyl ammonium hydroxide such; ammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, and the like.
  • tetraalkylammonium hydroxide is preferable because it is excellent in compatibility with glycols and amide organic solvents, and a cleaning liquid with little corrosion to metals can be obtained.
  • the content ratio of the quaternary ammonium hydroxide in the cleaning liquid is 2 to 10% by mass, preferably 2 to 5% by mass, more preferably 2 to 4% by mass.
  • the cleaning liquid is excellent in the decomposability of the organic matter and has little corrosion on the metal. 1-2.
  • glycols in the cleaning liquid in a content (mass) of 5 times or more with respect to the quaternary ammonium hydroxide, the organic substance decomposing ability of the cleaning liquid is increased, and the copper on the substrate to be processed And corrosion of metals such as aluminum can be suppressed.
  • glycols examples include ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol; propylene glycols such as propylene glycol, dipropylene glycol, tripropylene glycol, and polypropylene glycol; Among these, propylene glycols are preferable from the viewpoint of little corrosion on metals.
  • the molecular weight of glycols is 62 to 1000, preferably 76 to 600.
  • the viscosity of the cleaning agent is preferably within a range that is easy to handle.
  • the content (mass) of glycols contained in the cleaning liquid is 5 times or more, preferably 5 to 20 times, more preferably 10 to 17 times, more preferably the content (mass) of the quaternary ammonium hydroxide. Preferably it is 13 to 15 times.
  • the content of glycols has the above-mentioned upper limit, when the content of quaternary ammonium hydroxide is large, the content of glycols is relatively large, and is contained in the cleaning liquid. This is because the content of the amide-based organic solvent decreases, and there is a possibility that the time required for removing the decomposition products may be extended.
  • the content ratio of glycols contained in the cleaning liquid is relatively determined by the content ratio of the quaternary ammonium hydroxide, but is usually 10 to 60% by mass, preferably 15 to 50% by mass, and more preferably. Is 18 to 45 mass%. 1-3.
  • Amide-based organic solvent The amide-based organic solvent has a function of washing out an acid generated from a resist decomposed by a quaternary ammonium hydroxide.
  • amide organic solvents include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethyl Acetamide, N, N-diethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-octyl-2-pyrrolidone, N-cyclohexyl-2 -Pyrrolidone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropanamide, and N ', N-dimethylimidazolidinone Etc.
  • amide organic solvent As an amide organic solvent, it is excellent in compatibility with quaternary ammonium hydroxides and glycols, and also has an effect of washing out decomposition products such as acids generated from organic materials decomposed by quaternary ammonium hydroxides. Therefore, at least one amide organic solvent selected from a compound represented by the following formula (1) and a compound represented by the following formula (2) is preferable.
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 4 to 10 carbon atoms.
  • X is a methylene group or a divalent group represented by —NR 2 —.
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 3.
  • R 3 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group in which a hydrogen atom of an alkyl group having 1 to 6 carbon atoms is substituted with an alkoxy group having 1 to 6 carbon atoms.
  • R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • alkyl group having 1 to 8 carbon atoms in R 1 include a methyl group, a propyl group, an n-butyl group, and a tert-butyl group.
  • cycloalkyl group having 4 to 10 carbon atoms in R 1 include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • R 1 is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • Examples of the alkyl group having 1 to 8 carbon atoms in R 2 include a methyl group, a propyl group, an n-butyl group, and a tert-butyl group.
  • R 2 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • Examples of the alkyl group having 1 to 6 carbon atoms in R 3 include a methyl group, a propyl group, an n-butyl group, a tert-butyl group, and a hexyl group.
  • Examples of the group in which the hydrogen atom of the alkyl group having 1 to 6 carbon atoms in R 3 is substituted with an alkoxy group having 1 to 6 carbon atoms include a methoxy group, a butoxy group, and a hexyloxy group.
  • Examples of the alkyl group having 1 to 4 carbon atoms for R 4 include a methyl group, a propyl group, an n-butyl group, and a tert-butyl group. Among these, as R 3 , a methoxy group, a butoxy group, and a hexyloxy group are preferable.
  • highly safe amide organic solvent examples include 2-pyrrolidone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, and 3-hexyloxy-N, N-dimethylpropane. Examples include amides.
  • the content of the amide organic solvent in the cleaning liquid is 90 to 100% by mass, preferably 90 to 100% by mass when the remaining content of the cleaning liquid excluding the quaternary ammonium hydroxide and the glycol is 100% by mass. 95 to 100% by mass, more preferably 100% by mass.
  • the cleaning agent of the present invention is a cleaning liquid substantially consisting of a quaternary ammonium hydroxide, a glycol and an amide organic solvent. 1-4.
  • the other component cleaning liquid may contain other components generally used in the cleaning liquid as long as the function of the cleaning liquid is not impaired.
  • a surfactant for improving the wettability to the substrate to be processed an antifoaming agent for eliminating the bubbles in the cleaning liquid, a corrosion inhibitor for preventing the corrosion of the metal of the substrate to be processed, Metal chelating agents for protecting the metal of the substrate to be processed, organic solvents for adjusting the viscosity of the cleaning liquid (excluding the amide organic solvent), basic compounds other than quaternary ammonium hydroxides, etc.
  • a surfactant for improving the wettability to the substrate to be processed an antifoaming agent for eliminating the bubbles in the cleaning liquid
  • a corrosion inhibitor for preventing the corrosion of the metal of the substrate to be processed
  • Metal chelating agents for protecting the metal of the substrate to be processed organic solvents for adjusting the viscosity of the cleaning liquid (excluding the amide organic solvent), basic compounds other than quaternary ammonium hydroxides, etc.
  • the cleaning liquid of the present invention is characterized by substantially not containing water, it is preferable that water is not contained as much as possible. 1-5.
  • Preparation Method of Cleaning Solution Quaternary ammonium hydroxide is unstable on its own, and is usually commercially available in the form of an aqueous solution or a lower alcohol solution such as methanol. When the cleaning liquid is prepared in the state of such an aqueous solution or lower alcohol solution, as a result, the cleaning liquid contains a large amount of water or lower alcohol. For this reason, it is preferable that the solvent of the quaternary ammonium hydroxide solution can be uniformly dissolved from water or a lower alcohol with a component contained in the cleaning liquid, which can uniformly dissolve the quaternary ammonium hydroxide. .
  • components that can uniformly dissolve the quaternary ammonium hydroxide and that are included in the cleaning liquid include the glycols and the amide organic solvents.
  • the glycols can uniformly dissolve the quaternary ammonium hydroxide, are essential components of the cleaning liquid of the present invention, and are easy to prepare the cleaning liquid. ,preferable.
  • the washing liquid can be prepared by mixing the above.
  • insoluble materials and foreign substances such as metal ions can be removed with a filter such as a capsule filter or a membrane filter. Further, in order to remove moisture, moisture can be removed with a moisture removing agent such as magnesium sulfate.
  • the semiconductor substrate cleaning method of the present invention is a method of cleaning a semiconductor substrate using the cleaning liquid of the present invention. Specifically, organic substances such as resist residues are removed by bringing the cleaning agent of the present invention into contact with a semiconductor substrate after exposure, development, processing, or CMP processing after processing.
  • the cleaning liquid of the present invention can be used as a resist remover.
  • the semiconductor substrate can be washed and dried according to a general method.
  • Examples of the semiconductor substrate include a semiconductor wafer having a metal such as copper, aluminum, gold, and ITO, and a glass substrate.
  • the contact method includes a dipping method, a shower method, a liquid filling method, and the like. Among these, it is preferable when the dip method is performed by a batch method. Further, when the cleaning liquid is brought into contact with the cleaning liquid, it is possible to irradiate the cleaning liquid with ultrasonic waves in order to promote the decomposition of the organic matter.
  • the temperature of the cleaning liquid when contacting the cleaning liquid is usually 20 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C.
  • Examples of the resist include chemically amplified positive resists described in JP-A-2001-281862, JP-A-2008-058710, and JP-A-2006-267475; JP-A-2006-154434, and JP-A-2006-154434.
  • negative resists using chemical amplification chemically amplified negative resists described in JP 2011-123225 A, JP 2009-222923 A, JP 2006-243161 A, and the like.
  • the semiconductor substrate cleaning method of the present invention is a negative resist that is excellent in the decomposability of organic matter and has little corrosion on metals, and is difficult to remove, particularly a negative resist using a photopolymerization initiator.
  • the semiconductor substrate cleaning method of the present invention can be applied to any resist thickness.
  • the semiconductor substrate cleaning method of the present invention is excellent in the decomposability of organic substances and has little corrosion on metals, so that the semiconductor of the present invention is applied to a resist having a film thickness of 10 ⁇ m or more which is difficult to remove. It is preferable to apply a substrate cleaning method.
  • the cleaning liquid of the present invention contains a large amount of a strong base such as a quaternary ammonium hydroxide, it can suppress the corrosion of the metal of the semiconductor substrate and is excellent in the decomposability of organic substances. For this reason, the cleaning liquid and the semiconductor substrate cleaning method of the present invention can be suitably used for fine processing of a semiconductor wafer or the like.
  • the metal pattern forming method of the present invention includes a step of forming a resist pattern on a substrate, a step of forming a metal film on the substrate based on the resist pattern, and a resist after forming the metal film. A step of removing the pattern with the cleaning liquid.
  • This metal pattern forming method is a method characterized by adopting a process using the semiconductor substrate cleaning method in place of the process performed in the conventional metal pattern forming method as the process of removing the resist pattern. is there.
  • the step of forming a resist pattern on the substrate and the step of forming a metal film in a pattern on the substrate based on the resist pattern may be the same as in the conventional method.
  • Comparative Examples 1B, 1C, 1D, 1E, Reference Examples 1, 3 to 6 In Comparative Example 1A, Comparative Examples 1C, 1D, 1E, Reference Examples 1, 3, and 4 were performed in the same manner as Comparative Example 1A, except that the components shown in Table 1 below were mixed in the proportions shown in Table 1 below. A cleaning solution was prepared.
  • Example 1A Mix the propylene glycol (B1) solution of tetramethylammonium hydroxide (A1 component) prepared in Reference Preparation Example 1 with propylene glycol (B1) and 2-pyrrolidone (C1) in the proportions shown in Table 1 below. Thus, the cleaning liquid of Example 1A was prepared.
  • Example 1B to 6B, 1C to 9C, 1D to 2D, 1E, Comparative Example 2C, Reference Examples 2 and 7 In Examples 1A, Examples 2B to 6B, 1C to 9C, 1D to 2D, and 1E were prepared in the same manner as in Example 1A, except that the components shown in Table 1 below were mixed in the proportions shown in Table 1 below. The cleaning liquids of Comparative Example 2C and Reference Examples 2 and 7 were prepared.
  • A1 Tetramethylammonium hydroxide
  • B1 Propylene glycol
  • B2 Polyethylene glycol (polystyrene equivalent weight average molecular weight 400)
  • B3 Dipropylene glycol
  • C1 2-pyrrolidone
  • C2 N-methyl-2-pyrrolidone
  • C3 N-ethyl-2-pyrrolidone
  • C4 N, N'-dimethylimidazolidinone
  • C5 3-methoxy-N, N-dimethyl Propanamide
  • D1 Water 2.
  • the evaluation method of the evaluation cleaning liquid is as follows. The evaluation results are shown in Table 1. 2-1.
  • a copper sputtered film having a thickness of 1000 mm was formed on a silicon substrate having a corrosive area of 4.5 cm 2 .
  • the silicon substrate having the copper sputtered film was immersed in 33 ml of cleaning liquid at 70 ° C.
  • the corrosivity was evaluated by the rate ( ⁇ / min) at which the copper sputtered film was corroded by the cleaning liquid.
  • a copper sputtered film having a thickness of 1000 mm was formed on a silicon substrate having an organic decomposable area of 4.5 cm 2 .
  • a resist having a film thickness of 12 ⁇ m is formed from a negative resist forming composition (trade name “JSR ELPAC TM THB-121N”, manufactured by JSR Corporation) using a photopolymerization initiator. Formed.
  • the resist was prepared by heating a coating film of a negative resist-forming composition at 90 ° C. for 5 minutes, and then exposing the entire surface with light of a wavelength of 365 nm at 1000 mJ / cm 2 with a high-pressure mercury lamp. It was obtained by contacting with an aqueous solution of methylammonium hydroxide for 90 seconds, washing with running water, and blowing with nitrogen.
  • the silicon substrate having the resist was immersed in 33 ml of cleaning liquid at 70 ° C.
  • the decomposability of the organic matter was evaluated based on the following criteria from the time of immersion until the time when the organic matter was decomposed by the cleaning liquid and visually confirmed that the organic matter disappeared.
  • a copper sputtered film having a thickness of 1000 mm was formed on a silicon substrate having an area of 21 cm 2 in use .
  • a resist having a film thickness of 12 ⁇ m is formed from a negative resist forming composition (trade name “JSR ELPAC TM THB-121N”, manufactured by JSR Corporation) using a photopolymerization initiator. Formed.
  • the resist was prepared by heating a coating film of a negative resist-forming composition at 90 ° C. for 5 minutes, and then exposing the entire surface with light of a wavelength of 365 nm at 1000 mJ / cm 2 with a high-pressure mercury lamp.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
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  • Inorganic Chemistry (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
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  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

La présente invention vise à fournir un liquide nettoyant qui ne contient sensiblement pas d'eau, qui présente une excellente décomposition des matières organiques et qui présente une faible corrosion des métaux. La présente invention atteint ce but grâce à un agent nettoyant ne contenant sensiblement pas d'eau, caractérisé en ce qu'il contient 2 à 10 % en masse d'un hydroxyde d'ammonium quaternaire, et en outre un glycol et un solvant organique à base d'un amide ; et la teneur (en masse) du glycol étant au moins cinq fois supérieure à la teneur (en masse) de l'hydroxyde d'ammonium quaternaire.
PCT/JP2014/081545 2013-12-03 2014-11-28 Liquide nettoyant, procédé de nettoyage d'un substrat semi-conducteur, et procédé de formation d'un motif métallique WO2015083636A1 (fr)

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JP2013-249818 2013-12-03
JP2013249818A JP2017026645A (ja) 2013-12-03 2013-12-03 レジスト除去剤およびレジスト除去方法

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