WO2016068290A1 - フォトレジスト残渣および/またはポリマー残渣を除去するための組成物 - Google Patents
フォトレジスト残渣および/またはポリマー残渣を除去するための組成物 Download PDFInfo
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- WO2016068290A1 WO2016068290A1 PCT/JP2015/080739 JP2015080739W WO2016068290A1 WO 2016068290 A1 WO2016068290 A1 WO 2016068290A1 JP 2015080739 W JP2015080739 W JP 2015080739W WO 2016068290 A1 WO2016068290 A1 WO 2016068290A1
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- H10P70/273—
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- 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
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- 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
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/042—Acids
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
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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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
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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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
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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
- 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
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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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
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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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5022—Organic solvents containing oxygen
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- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
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- 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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
- H01L21/32138—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only pre- or post-treatments, e.g. anti-corrosion processes
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- H10P50/269—
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- H10P52/00—
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- H10P76/00—
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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
- 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 composition for removing a photoresist residue and / or a polymer residue remaining after dry etching, chemical etching or ashing in a manufacturing process of a semiconductor circuit element having a metal wiring, and a residue using the composition It relates to a removal method.
- the composition for removing a photoresist residue and / or a polymer residue remaining after dry etching and ashing includes an inorganic alkali, an organic alkali, an inorganic acid, an organic acid, A composition in which an inorganic acid salt, an organic acid salt or the like is used as a main material and mixed with water, a water-soluble solvent, a complexing agent, a chelating agent, a surfactant, or the like is used.
- compositions for removing the photoresist residue and / or polymer residue remaining after dry etching or ashing a composition containing an amine compound is often used.
- the metal surface such as aluminum or tungsten on the substrate, the metal thin film or the like is easily corroded, and the metal surface is corroded.
- strong alkali may be exhibited due to the action of the amine compound and water, and the metal wiring material may be corroded. This can be dealt with by rinsing with isopropyl alcohol or the like before washing with water, but the work process is increased and complicated.
- Patent Document 1 discloses an aqueous solution composition containing an alkanolamine and an organic acid
- Patent Document 2 discloses an aqueous solution composition containing phosphoric acid and a primary to quaternary amine.
- Patent Documents 3 and 4 report an aqueous solution composition containing an amine having a chelating effect, an acid, and a salt thereof
- Patent Document 5 reports a composition containing piperazine.
- Patent Document 6 includes an aqueous polycarboxylic acid and a salt thereof and an aminopolycarboxylic acid and an aqueous solution composition containing at least one of the salts
- Patent Document 7 includes a polyvalent carboxylate and a glycol ether.
- a composition of an aqueous solution is reported in Patent Document 8 as an aqueous solution composition containing an organic acid and / or a salt thereof and an organic solvent.
- Patent Document 9 reports an aqueous solution composition containing ammonium phosphate.
- a composition containing a fluoride such as hydrofluoric acid or ammonium fluoride is excellent in removal of a residue containing a metal oxide.
- the composition containing fluoride the composition of an aqueous solution containing an anticorrosive of ammonium fluoride, a polar solvent, and an acidic compound is disclosed in Patent Document 10, and the composition containing a fluorine compound and an ether solvent is disclosed in Patent Document 12.
- Patent Document 13 describes a highly alkaline microelectronic substrate cleaning composition having a pH exceeding 11.5 and containing saccharin as a liquid bath stabilizer.
- Patent Documents 14 and 15 describe semiconductor substrate cleaning liquids containing fluoride, and saccharic acid as an example of a chelating agent that promotes dissolution of metal residues that may be contained.
- Patent Document 16 describes a microelectronic cleaning solution containing at least one of ammonium and quaternary ammonium ions and hypophosphorous acid and phosphite ions as essential components, and saccharic acid as an example of a corrosion inhibitor. ing.
- none of the documents has specifically studied a composition containing saccharic acid.
- JP-A-11-174690 Japanese Patent Laid-Open No. 2002-176041 JP 2003-223010 A JP 2001-51429 A Japanese Patent Laid-Open No. 2004-205673 JP-A-11-316464 JP 2004-94034 A JP 2000-206709 A Japanese Patent Laid-Open No. 2000-233203 JP 2000-260761 A Japanese Patent Laid-Open No. 2001-100136 JP 2004-239966 A JP 2014-84464 A JP-T-2004-511917 JP 2008-198994 A Special Table 2007-503115
- the above-mentioned conventional techniques have problems such as insufficient residue removability and corrosion of metal wiring, and satisfactory results are still obtained when focusing on residue removability and corrosion resistance of each material. Absent.
- the composition described in Patent Document 1 has an anticorrosive property for metal wiring
- the compositions described in Patent Documents 2 to 5 have a residue removal property and an anticorrosive property for metal wiring. Then, each residue removal property is insufficient.
- the composition described in Patent Document 9 is preferable in terms of work because it does not contain deleterious substances or poisonous substances and does not belong to dangerous materials, but its characteristics are insufficient when focusing on residue removal and corrosion resistance of metal wiring It is.
- the compositions described in Patent Documents 10 to 12 are not satisfactory in terms of the corrosion resistance of metal wiring.
- an object of the present invention is to solve the above-mentioned problems, and to remove a photoresist residue and / or a polymer residue generated in a manufacturing process of a semiconductor circuit element having a metal wiring, and a photoresist using the same It is an object to provide a method for removing a residue and / or polymer residue, a method for producing a semiconductor circuit element having a metal wiring including a step of using the removal method, and a semiconductor circuit element produced by the method.
- the present inventor has included water, water-soluble solvent, acid, and dissociation in order to remove the photoresist residue and / or polymer residue remaining after wiring formation of various metals.
- a composition in which nitrogen compounds are appropriately combined is effective, but has faced problems such as insufficient residue removal and corrosion of metal wiring materials.
- the present inventor remarkably improves the removability of the photoresist residue and / or polymer residue without corroding the metal wiring material by incorporating saccharin into the solution, particularly at a pH of 9.7 or less. As a result of finding that it can be improved and further researching it, the present invention has been completed.
- the present invention relates to the following.
- a composition for removing a photoresist residue and / or a polymer residue comprising saccharin and water and having a pH of 9.7 or less.
- the method according to [1] further including one or more substances selected from the group consisting of (A) a water-soluble solvent, (B) an acid, and (C) a dissociable nitrogen-containing compound.
- Composition [3] The composition according to [1] or [2], wherein the saccharin content is 0.01% by mass or more.
- [4] A method for removing a photoresist residue and / or a polymer residue using the composition according to any one of [1] to [3].
- [5] A method of manufacturing a semiconductor circuit element having metal wiring, The method comprising the step of removing a photoresist residue and / or a polymer residue remaining in a structure for forming a metal wiring, using the composition according to any one of [1] to [3].
- [6] A semiconductor circuit element manufactured by the manufacturing method according to [5].
- a saccharin is contained in a composition for removing a photoresist residue and / or a polymer residue, particularly at a pH of 9.7 or less, so that a photoresist residue after dry etching or chemical etching is obtained.
- the removability of the polymer residue is greatly improved, and the selectivity between the residue removal and the etching of the metal wiring material is increased.
- saccharin not only has the ability to remove photoresist residues and / or polymer residues containing a polymer component as an active ingredient, but also suppresses corrosion of Al—Cu and the like during the removal of the residue, and changes the state of Al—Cu and the like.
- the photoresist residue and / or polymer residue on the substrate can be easily removed without corroding the metal wiring material.
- FIG. 1 is a schematic cross-sectional view of a part of an Al—Cu wiring.
- a composition for removing a photoresist residue and / or a polymer residue is obtained by performing etching using a photoresist as a mask and further performing ashing in a manufacturing process of a semiconductor circuit element having a metal wiring. Used to remove photoresist residues and / or polymer residues remaining on a semiconductor substrate, and photoresist residues and / or polymer residues remaining on a semiconductor substrate after dry etching or chemical etching using an inorganic material as a mask be able to.
- photoresist residue refers to a material containing a photoresist-derived component remaining after a photoresist mask peeling process such as a photolithography process, an etching process, and an ashing process using a photoresist as a mask.
- the photoresist residue includes a reaction product generated by reaction of the photoresist by etching or ion implantation, an unreacted photoresist, a photoresist ashed by ashing, and the like.
- the “polymer residue” refers to a deposit of a reaction product of the material to be etched and the etching gas that remains as a by-product on the wall surface of the material to be etched during dry etching.
- the polymer residue may include an organic substance such as a polymer component derived from a photoresist, a component derived from an etching gas, a component derived from a material to be etched, and an inorganic substance such as a metal residue.
- organic substance such as a polymer component derived from a photoresist, a component derived from an etching gas, a component derived from a material to be etched, and an inorganic substance such as a metal residue.
- Specific examples include a sidewall polymer (also referred to as a sidewall protective film or a rabbit ear) generated when forming metal wiring, a sidewall polymer generated when dry etching the interlayer insulating film, and remains on the side and bottom surfaces of the via hole when forming the via hole.
- examples include polymers containing organometallic polymers and metal oxides.
- the “metal residue” includes a component derived from a material of a metal wiring generated by etching. For example, metals
- composition for removing the photoresist residue and / or polymer residue of the present invention comprises saccharin and water, and if necessary, (A) a water-soluble solvent, (B) an acid, and (C) a dissociable material. Contains one or more substances selected from the group consisting of nitrogen-containing compounds. Further, a surfactant may be included.
- the pH of the composition for removing the photoresist residue and / or polymer residue of the present invention is preferably 9.7 or less, more preferably pH 9.0 or less, particularly preferably pH 0.0 or more and pH 9.0 or less. is there. More preferably, it is pH 1.0 or more and pH 7.0 or less from the viewpoint of residue removability, corrosion resistance of metal wiring material, selectivity of residue removal and etching of metal wiring material, and the like. When the pH exceeds 9.8, corrosion of Al—Cu, which is a metal wiring material, is likely to occur, and residue removability decreases.
- the pH can be adjusted using ammonia, primary amine, secondary amine, tertiary amine, quaternary ammonium hydroxide, inorganic acid, organic acid or the like.
- the content of saccharin contained in the composition for removing the photoresist residue and / or polymer residue of the present invention is not particularly limited, but it is possible to remove the photoresist residue and / or polymer residue and to prevent corrosion of the metal wiring material. Therefore, the saccharin content is preferably 0.01% by mass or more. In the case of a composition comprising saccharin and water, the saccharin content is preferably 0.01 to 0.40% by mass. More preferably, the content is 0.01 to 0.20% by mass. In addition to saccharin and water, the saccharin content is 0.01 if the composition contains at least one from the group of (A) a water-soluble solvent, (B) acid, and (C) a dissociable nitrogen-containing compound. ⁇ 20% by weight is preferred. More preferably, it is 0.05 to 5% by mass. Moreover, there is no restriction
- water-soluble solvent used in the composition for removing the photoresist residue and / or polymer residue of the present invention examples include alcohols, glycol ethers, esters, amides, and lactams.
- Other examples include sulfur-containing compounds such as dimethyl sulfoxide and sulfolane. You may use these 1 type or in mixture of 2 or more types.
- the content of the water-soluble solvent is not particularly limited, but is preferably 1 to 99% by mass, more preferably 1 to 50% by mass, from the viewpoints of removal of photoresist residues and / or polymer residues and corrosion prevention of metal wiring materials. It is.
- Examples of the alcohols include alcohols having an ether group such as furfuryl alcohol and tetrahydrofurfuryl alcohol, and glycols.
- Examples of glycols include ethylene glycol (1,2-ethanediol), propylene glycol (1,2-propanediol), 1,3-propanediol, diethylene glycol (3-oxapentane-1,5-diol), diethylene glycol Propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, glycerin (1,2,3-propanetriol), hexylene glycol (2-methyl) -2,4-pentanediol).
- tetrahydrofurfuryl alcohol, propylene glycol (1,2-propanediol), hexylene glycol (2-methyl-2,4-pentanediol) or a mixture thereof is preferable.
- glycol ethers ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether , Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene Recall monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol mono
- Esters include carboxylic acid esters, carbonate esters, lactones, phosphate esters, and sulfate esters. You may use these 1 type or in mixture of 2 or more types.
- Carboxylic acid esters include methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl lactate, ethyl lactate, propyl lactate, ethyl 2-hydroxybutyrate, dimethyl malate, diethyl malate, dimethyl tartrate, diethyl tartrate, diisopropyl tartrate, And propyl lactate. Of these, ethyl lactate is preferable.
- Examples of the carbonate ester include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, and propylene carbonate. Of these, ethylene carbonate and propylene carbonate are preferable.
- Lactones include ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -valerolactone. Of these, ⁇ -butyrolactone is preferred.
- amide examples include acetamide, N-methylacetamide, isobutyric acid amide, propionic acid amide, N-ethylacetamide, malonamide, nicotinamide, and N, N-dimethylacetamide. Of these, N, N-dimethylacetamide is preferred.
- Lactams include N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone. Of these, 1,3-dimethyl-2-imidazolidinone is preferred.
- the acid used in the composition for removing the photoresist residue and / or polymer residue of the present invention includes an inorganic acid and an organic acid.
- the content of the acid is not particularly limited, but is preferably 0.001 to 90% by mass, more preferably from the viewpoint of the removability of the composition for removing the photoresist residue and / or polymer residue and the corrosion protection of the wiring material. Is 0.002 to 30% by mass.
- inorganic acids include hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydrosulfuric acid, etc., phosphoric acid, diphosphoric acid, tripolyphosphoric acid, boric acid, iodic acid, sulfuric acid, sulfurous acid, hypochlorous acid, hypochlorous acid Examples include acid, perchloric acid, nitric acid, nitrous acid, peroxonitric acid, peroxophosphoric acid, peroxodiphosphoric acid, peroxosulfuric acid, peroxodisulfuric acid, and hydrogen peroxide. You may use these 1 type or in mixture of 2 or more types. Preferred is hydrofluoric acid, phosphoric acid, diphosphoric acid, boric acid or a mixture thereof, and particularly preferred is hydrofluoric acid, phosphoric acid or a mixture thereof.
- organic acids include carboxylic acids and phenols.
- sulfonic acids such as methanesulfonic acid and phosphonic acids such as nitrilotris (methylenephosphonic acid). You may use these 1 type or in mixture of 2 or more types.
- carboxylic acids include formic acid, acetic acid, methoxyacetic acid, trifluoroacetic acid, propionic acid, butyric acid, lactic acid, malic acid, citric acid, glycolic acid, glyoxylic acid, oxalic acid, malonic acid, succinic acid, and maleic acid. Can be mentioned. You may use these 1 type or in mixture of 2 or more types. Acetic acid, lactic acid, malonic acid, methoxyacetic acid or a mixture thereof is preferable, and acetic acid, lactic acid, malonic acid or a mixture thereof is particularly preferable.
- phenols examples include phenol, catechol, pyrogallol, salicylic acid, guaiacol, and gallic acid. You may use these 1 type or in mixture of 2 or more types. Among these, catechol, gallic acid or a mixture thereof is preferable.
- Examples of the dissociable nitrogen-containing compound used in the composition for removing the photoresist residue and / or polymer residue of the present invention include ammonia, ammonium salt, amine, amine salt, quaternary ammonium salt, and amino acids. You may use these 1 type or in mixture of 2 or more types.
- the content of the dissociative nitrogen-containing compound is not particularly limited, but is preferably 0.005 to 50% by mass, and more preferably 0 from the viewpoint of removal of a photoresist residue and / or polymer residue and corrosion protection of the wiring material. 0.005 to 35% by mass.
- ammonium salts include organic ammonium salts and inorganic ammonium salts.
- Organic ammonium salts include ammonium salts of carboxylic acids such as ammonium acetate, ammonium oxalate, ammonium citrate, and ammonium tartrate.
- Inorganic ammonium salts include ammonium sulfate, triammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium chloride, and ammonium fluoride. You may use these 1 type or in mixture of 2 or more types. Among these, ammonium oxalate, diammonium hydrogen phosphate, ammonium fluoride, or a mixture thereof is preferable.
- amines examples include hydroxylamine, alkanolamine, alkylamine, and cyclic amine. You may use these 1 type or in mixture of 2 or more types.
- alkanolamine examples include monoethanolamine, isopropanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine, and N, N-dimethylmonoethanolamine. Of these, monoethanolamine is preferable.
- Alkylamines include methylamine, dimethylamine, trimethylamine, tert-butylamine, ethylamine, diethylamine, isopropylamine, diisopropylamine, 1,1-dimethylhydrazine, N, N-dimethylethylamine, N, N-diethylmethylamine, N , N-dimethylisopropylamine, ethylenediamine, ethylmethylamine, 1,2-dimethylpropylamine, butylamine, isobutylamine, propylamine, N, N, N′N′-tetramethylethylenediamine, 1,2-diaminopropane, 1, , 3-diaminopropane, N, N-dimethylethylenediamine. You may use these 1 type or in mixture of 2 or more types. Of these, diisopropylamine is preferable.
- cyclic amines examples include imidazole, pyridine, pyrazine, pyrimidine, piperazine, morpholine, purine, and derivatives thereof. You may use these 1 type or in mixture of 2 or more types. Among these, imidazole, piperazine or a mixture thereof is preferable.
- Amine salts include piperazine sulfate, hydroxylamine sulfate, guanidine phosphate, triethanolamine phosphate, piperazine phosphate, piperazine citrate, phenylhydrazine oxalate, 2- (dimethylamino) ethanol L-tartaric acid, L- (+)-L hydrazine tartrate, piperazine dihydrochloride, hydroxylamine hydrochloride, monoethanolamine hydrochloride, diethanolamine hydrochloride, triethanolamine hydrochloride. You may use these 1 type or in mixture of 2 or more types. Among these, hydroxylamine sulfate, guanidine phosphate, piperazine phosphate or a mixture thereof is preferable.
- Quaternary ammonium salts include tetramethylammonium hydroxide, tetramethylammonium fluoride, tetramethylammonium tetrafluoroborate, tetramethylammonium hexafluorophosphate, tetramethylammonium sulfate, tetramethylammonium chloride, tetrachloric acid tetra Methylammonium, tetramethylammonium acetate, tetraethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium fluoride, choline, choline chloride, choline bitartrate, triethylmethylammonium tetrafluoroborate, tetrapropylammonium hydroxide, tetrapropylammonium chloride , Tetrabutylammonium hydroxide, tetrabutyla Monium
- Amino acids include alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, citrulline, bicine, Examples include iminodiacetic acid. You may use these 1 type or in mixture of 2 or more types. Of these, glycine is preferable.
- a cationic, anionic or nonionic surfactant may be added to the composition for removing the photoresist residue and / or polymer residue of the present invention.
- content of surfactant is not specifically limited, Less than 0.3 mass% is preferable.
- the treatment temperature and the treatment time may be appropriately adjusted.
- the treatment temperature is adjusted to 25 ° C. to 70 ° C., and the treatment time is adjusted in the range of 10 seconds to 30 minutes.
- ultrapure water As the rinse liquid after using the composition for removing the photoresist residue and / or polymer residue of the present invention, ultrapure water, a water-soluble solvent, or a mixed liquid of ultrapure water and a water-soluble solvent can be used.
- water-soluble solvent methyl alcohol, ethyl alcohol, and isopropanol are generally used, but other water-soluble solvents may be used.
- the composition of the present invention can be used without particular limitation for commonly used photoresists.
- the present invention relates to a method for removing a photoresist residue and / or a polymer residue using the composition of the present invention.
- it is a method for producing a semiconductor circuit element having a metal wiring using the method, and using the composition of the present invention, a photoresist residue and / or a polymer residue remaining in a structure for forming the metal wiring
- the method comprising the step of removing.
- the “structure for forming metal wiring” means a structure at any metal wiring process stage in the process of manufacturing a semiconductor circuit element having metal wiring.
- a structure at a stage where etching is further performed after the photolithography process a structure at a stage where ashing is performed, a structure at a stage where etching is further performed after ashing, and the like can be given. More specifically, the structure after the dry etching treatment of the interlayer insulating film, the structure after the via hole is formed, the structure shown in FIG.
- composition for removing the photoresist residue and / or polymer residue of the present invention will be described in more detail with reference to examples and comparative examples.
- the present invention is not limited to these examples.
- FIG. 1 shows a cross section of a part of an Al—Cu wiring formed on a silicon wafer by dry etching using a photoresist as a mask and removing the resist by oxygen plasma.
- a positive type photoresist was used as the photoresist.
- Photoresist residue and polymer residue (2) are attached to the upper and side surfaces of the Al—Cu (1) wiring.
- the barrier metal is composed of titanium (3) and titanium nitride (4), and the substrate is composed of silicon (5) and silicon oxide film (6). Using this substrate, the residue removal property and the corrosion resistance of Al—Cu were evaluated.
- the evaluation method is as follows.
- compositions comprising water, water and water-soluble solvents, water and acids, water and dissociable nitrogen-containing compounds (Table 2 Comparative Examples 1 to 32) and compositions obtained by adding saccharin to these compositions (Table 1 Example 1) Evaluation was performed on ⁇ 32).
- residue removal was insufficient or corrosion of the Al—Cu part of the metal wiring was confirmed (Table 4).
- the compositions for removing photoresist residues and / or polymer residues according to the present invention (Examples 1 to 32) showed good residue removability, and the state of the Al—Cu portion of the metal wiring was also good. It was good (Table 3).
- saccharin is added to each composition comprising water, water and water-soluble solvent, water and acid, and water and dissociable nitrogen-containing compounds, residue removal is improved and between residue removal and Al-Cu etching. It was confirmed that the selectivity was improved.
- the active ingredient of the composition for removing conventional photoresist residues and / or polymer residues includes fluorine compounds such as hydrofluoric acid and ammonium fluoride, phenols typified by catechol, amino acids such as glycine and iminodiacetic acid And amines such as triethanolamine, and organic acids such as phosphoric acid and acetic acid.
- fluorine compounds such as hydrofluoric acid and ammonium fluoride
- phenols typified by catechol
- amino acids such as glycine and iminodiacetic acid And amines such as triethanolamine
- organic acids such as phosphoric acid and acetic acid.
- compositions for removing conventional photoresist residues and / or polymer residues containing these active ingredients (Table 10 Comparative Examples 46 to 63) and compositions for removing conventional photoresist residues and / or polymer residues The composition in which saccharin was added instead of the active ingredient (Table 9, Examples 46 to 56) was evaluated, and the effect of the active ingredient of the conventional composition was compared with the effect of saccharin. In Comparative Examples 46 to 63, it was confirmed that the residue removal was insufficient or the Al—Cu part of the metal wiring was corroded (Table 12).
- compositions for removing photoresist residues and / or polymer residues according to the present invention showed good residue removability, and the state of the Al—Cu portion of the metal wiring was also good. It was good (Table 11). It has been confirmed that saccharin exhibits an effect superior to the active ingredient of the composition for removing conventional photoresist residues and / or polymer residues.
- An aqueous solution composed of triammonium phosphate and ammonia (Comparative Example 64, pH 9.8), a composition composed of triammonium phosphate, saccharin and water (Example 57, pH 8.9), triammonium phosphate, ammonia, saccharin and water
- the resulting composition (Example 58, pH 9.0) was evaluated. Good results were obtained with a composition consisting of triammonium phosphate having a pH of 8.9, saccharin and water (Example 57). Similarly good results were obtained with a composition comprising triammonium phosphate having a pH of 9.0, ammonia, saccharin and water (Example 58).
- Al—Cu was corroded and residue removal was insufficient.
- Example 65 An aqueous solution composed of propylene carbonate, hydrofluoric acid and water (Comparative Example 65) and a composition composed of propylene carbonate, hydrofluoric acid, water and saccharin (Example 59) were evaluated at low pH.
- the actual etching rate of Example 59 is 0.01 to 0.02 nm / min
- the actual etching rate of Comparative Example 65 is 0.04 nm / min
- the etching rate is reduced by adding saccharin, that is, An improvement in the corrosion resistance of Al—Cu was observed.
- the removability of the residue was improved, and an improvement in the selectivity between residue removal and Al—Cu etching was observed.
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Abstract
Description
一方、特許文献13には、サッカリンを液浴安定剤として含むpH11.5を超える高アルカリ性のマイクロエレクトロニクス基板洗浄用組成物が記載されている。
また特許文献14および15には、フッ化物を含む半導体基板洗浄液が記載され、含有し得る金属残渣の溶解を促進するキレート剤の一例としてサッカリン酸が記載されている。
特許文献16には、アンモニウムおよび第四級アンモニウムイオンの少なくとも一種、および次亜リン酸および亜リン酸イオンを必須成分とするマイクロエレクトロニクス洗浄液が記載され、腐食阻害剤の一例としてサッカリン酸が記載されている。しかしながら、いずれの文献もサッカリン酸を含む組成物についての具体的な検討はなされていない。
例えば、特許文献1に記載の組成物では金属配線の防食性が、特許文献2~5に記載の組成物では残渣除去性と金属配線の防食性が、特許文献6~8に記載の組成物では残渣除去性がそれぞれ不十分である。特許文献9に記載の組成物は、劇物、毒物を含まず、危険物にも属さないことから、作業面では好ましいが、残渣除去性と金属配線の防食性に着目するとその特性は不十分である。特許文献10~12に記載の組成物も、金属配線の防食性の点において満足できるものではない。
これに対し、本発明者はサッカリンを溶液に含有せしめることにより、特にpH9.7以下で含有せしめることにより、金属配線材料を腐食せずに、フォトレジスト残渣および/またはポリマー残渣の除去性を著しく向上できることを見出し、さらに研究を進めた結果、本発明を完成するに至った。
[1] サッカリンと水とを含み、pHが9.7以下であることを特徴とする、フォトレジスト残渣および/またはポリマー残渣を除去するための組成物。
[2] さらに(A)水溶性溶剤、(B)酸および(C)解離性の含窒素化合物からなる群から選択される1種または2種以上の物質を含む、前記[1]に記載の組成物。
[3] サッカリンの含有量が0.01質量%以上である、前記[1]または[2]に記載の組成物。
[5] 金属配線を有する半導体回路素子の製造方法であって、
前記[1]~[3]のいずれかに記載の組成物を用いて、金属配線を形成するための構造体に残存するフォトレジスト残渣および/またはポリマー残渣を除去する工程を含む、前記方法。
[6] 前記[5]に記載の製造方法で製造した半導体回路素子。
フォトレジスト残渣は、エッチングやイオン注入等によってフォトレジストが反応して生じた反応生成物、未反応のフォトレジスト、アッシングにより灰化されたフォトレジスト等を包含する。
また、「ポリマー残渣」とは、ドライエッチング時に被エッチング材料壁面に副生成物として残留する、被エッチング材料とエッチングガスの反応生成物の堆積物を示す。ポリマー残渣はフォトレジスト由来のポリマー成分などの有機物、エッチングガス由来の成分、被エッチング材料由来の成分、金属残渣などの無機物を含み得る。具体例には、金属配線の形成時に発生するサイドウォールポリマー(側壁保護膜、ラビットイヤーとも呼ばれる)、層間絶縁膜をドライエッチングする時に生じるサイドウォールポリマー、ビアホール形成時にビアホールの側面及び底面に残留する有機金属ポリマーおよび金属酸化物を含むポリマー等がある。
本発明において、前記「金属残渣」は、エッチングにより生じる金属配線の材料由来の成分を包含し、例えば銅、アルミニウム、チタン、タンタル、タングステン、ゲルマニウム、アンチモンおよびテルル等の金属、ならびに、これらの酸化物およびハロゲン化物を包含する。
pHの調整は、アンモニア、第一級アミン、第二級アミン、第三級アミン、第四級アンモニウム水酸化物、無機酸、有機酸などを用いて行うことができる。
中でも、テトラヒドロフルフリルアルコール、プロピレングリコール(1,2-プロパンジオール)、へキシレングリコール(2-メチル-2,4-ペンタンジオール)またはこれらの混合物が好ましい。
本発明は、一側面において、本発明の組成物を用いた、フォトレジスト残渣および/またはポリマー残渣を除去する方法に関する。
また該方法を用いた金属配線を有する半導体回路素子を製造する方法であって、本発明の組成物を用いて、金属配線を形成するための構造体に残存するフォトレジスト残渣および/またはポリマー残渣を除去する工程を含む、前記方法に関する。
例えば、フォトリソグラフィー処理後さらにエッチング処理された段階の構造体、アッシング処理された段階の構造体、アッシング後さらにエッチング処理された段階の構造体などが挙げられる。より具体的には層間絶縁膜のドライエッチング処理後の構造体およびビアホール形成後の構造体、図1に示した構造体などが挙げられる。
シリコンウェハー上に、フォトレジストをマスクとしてドライエッチング、酸素プラズマによるレジスト除去を行い形成したAl-Cuの配線の一部分の断面を図1に示した。フォトレジストはポジ型フォトレジストを使用した。Al-Cu(1)の配線の上部と側面には、フォトレジスト残渣およびポリマー残渣(2)が付着している。なお、バリアメタルは、チタン(3)、窒化チタン(4)、基板はシリコン(5)、シリコン酸化膜(6)により構成されている。この基板を用いて、残渣除去性とAl-Cuの防食性を評価した。評価方法は以下のとおりである。
基板を表1、表2、表5、表6、表9、表10、表13、表14、表17および表18に示した評価薬液に浸漬させた後、超純水でリンスを行い、乾燥した。これを電子顕微鏡(SEM)で観察して、Al-Cuの配線の状態を確認した。薬液処理条件は各評価薬液の特性を考慮して、適切な条件とした。処理温度は25℃~70℃、処理時間は10秒~30分の範囲とした。超純水リンスの時間は1分とした。リンス後の乾燥は窒素ブローとした。評価結果を表7~12に示した。
水、水と水溶性溶剤、水と酸、水と解離性の含窒素化合物からなる各組成物にサッカリンを加えると、残渣除去性の向上し、且つ残渣除去とAl-Cuのエッチングとの間で選択性が向上することが確認された。
Claims (6)
- サッカリンと水とを含み、pHが9.7以下であることを特徴とする、フォトレジスト残渣および/またはポリマー残渣を除去するための組成物。
- さらに(A)水溶性溶剤、(B)酸および(C)解離性の含窒素化合物からなる群から選択される1種または2種以上の物質を含む、請求項1に記載の組成物。
- サッカリンの含有量が0.01質量%以上である、請求項1または2に記載の組成物。
- 請求項1~3のいずれか一項に記載の組成物を用いる、フォトレジスト残渣および/またはポリマー残渣を除去する方法。
- 金属配線を有する半導体回路素子の製造方法であって、
請求項1~3のいずれか一項に記載の組成物を用いて、金属配線を形成するための構造体に残存するフォトレジスト残渣および/またはポリマー残渣を除去する工程を含む、前記方法。 - 請求項5に記載の製造方法で製造した半導体回路素子。
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| SG11201701771YA SG11201701771YA (en) | 2014-10-31 | 2015-10-30 | Composition for removing photoresist residue and/or polymer residue |
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| JP4642001B2 (ja) * | 2006-10-24 | 2011-03-02 | 関東化学株式会社 | フォトレジスト残渣及びポリマー残渣除去液組成物 |
| US7879783B2 (en) | 2007-01-11 | 2011-02-01 | Air Products And Chemicals, Inc. | Cleaning composition for semiconductor substrates |
| US9536730B2 (en) | 2012-10-23 | 2017-01-03 | Air Products And Chemicals, Inc. | Cleaning formulations |
| KR102118964B1 (ko) * | 2012-12-05 | 2020-06-08 | 엔테그리스, 아이엔씨. | Iii-v 반도체 물질을 세척하기 위한 조성물 및 이를 사용하는 방법 |
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2014
- 2014-10-31 JP JP2014223642A patent/JP6501492B2/ja not_active Expired - Fee Related
-
2015
- 2015-10-30 SG SG11201701771YA patent/SG11201701771YA/en unknown
- 2015-10-30 TW TW104135802A patent/TWI674486B/zh not_active IP Right Cessation
- 2015-10-30 DE DE112015004958.4T patent/DE112015004958T5/de not_active Withdrawn
- 2015-10-30 WO PCT/JP2015/080739 patent/WO2016068290A1/ja not_active Ceased
- 2015-10-30 KR KR1020177005072A patent/KR20170078589A/ko not_active Withdrawn
- 2015-10-30 US US15/510,810 patent/US11091726B2/en not_active Expired - Fee Related
- 2015-10-30 CN CN201580046644.7A patent/CN106688081A/zh active Pending
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| WO2013101907A1 (en) * | 2011-12-28 | 2013-07-04 | Advanced Technology Materials, Inc. | Compositions and methods for selectively etching titanium nitride |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11380537B2 (en) * | 2016-12-14 | 2022-07-05 | Samsung Electronics Co., Ltd. | Method of manufacturing a semiconductor device and a cleaning composition for an adhesive layer |
| CN113430065A (zh) * | 2020-03-23 | 2021-09-24 | 上海新阳半导体材料股份有限公司 | 抗反射涂层清洗及刻蚀后残留物去除组合物、制备方法及用途 |
| CN113430065B (zh) * | 2020-03-23 | 2024-06-07 | 上海新阳半导体材料股份有限公司 | 抗反射涂层清洗及刻蚀后残留物去除组合物、制备方法及用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20170078589A (ko) | 2017-07-07 |
| US20180051237A1 (en) | 2018-02-22 |
| CN106688081A (zh) | 2017-05-17 |
| DE112015004958T5 (de) | 2017-07-27 |
| JP6501492B2 (ja) | 2019-04-17 |
| US11091726B2 (en) | 2021-08-17 |
| TWI674486B (zh) | 2019-10-11 |
| TW201629644A (zh) | 2016-08-16 |
| SG11201701771YA (en) | 2017-04-27 |
| JP2016092150A (ja) | 2016-05-23 |
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