Classifications

• • 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
• • 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
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/30—Amines; Substituted amines ; 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • 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
  • C11D3/044—Hydroxides or bases
• • 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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3947—Liquid compositions
• • 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
  • C11D3/395—Bleaching agents
  • C11D3/3955—Organic bleaching agents
• • 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
  • C11D3/395—Bleaching agents
  • C11D3/3956—Liquid compositions
• • 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
• • 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
  • C11D7/32—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
  • C11D7/22—Organic compounds
  • C11D7/32—Organic compounds containing nitrogen
  • C11D7/3281—Heterocyclic compounds
• • 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
  • C11D7/34—Organic compounds containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/50—Solvents
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
  • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
  • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
  • C23G1/20—Other heavy metals
• • 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
  • G03F7/30—Imagewise removal using liquid means
  • G03F7/32—Liquid compositions therefor, e.g. developers
• • 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
  • G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
• • 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
  • H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
• • 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
  • H01L21/31105—Etching inorganic layers
  • H01L21/31111—Etching inorganic layers by chemical means
  • H01L21/31116—Etching inorganic layers by chemical means by dry-etching
• • 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
  • 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
• • 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
  • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
  • H01L21/02052—Wet cleaning only
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S438/00—Semiconductor device manufacturing: process
  • Y10S438/906—Cleaning of wafer as interim step

Definitions

• the present invention relates to semiconductor processing and, more particularly, to photoresist removal.
• Integrated circuits are manufactured by a general sequence of steps wherein photoresist is coated onto a substrate, the photoresist layer is patterned by exposure and development, the pattern is transferred to the substrate, and the photoresist removed. This sequence of steps is repeated to build up multiple layers of patterned circuitry.
• photoresist removal step plasma ashing is commonly used since etched photoresist residues may be difficult or impossible to remove using only wet cleaning, especially without damaging other materials that are present.
• Positive photoresist is soluble in alkaline aqueous solutions as well as in compositions consisting of select organic and inorganic compounds.
• a gas-phase plasma etch such as a gas-phase plasma etch used for etching dielectric materials, will typically develop a hardened crust or residue, on the surface.
• the residue typically consists of cross-linked organic polymers, and may contain small amounts of silicon, metal, and halogen or other atoms.
• the plasma etch may be a fluorine-based plasma etch to etch silicate- based interlayer dielectric (ILD) materials. These materials may include silicates, organosilicates and fluorosilicates. Fluorine-based plasma etching may cause fluorination of the cross-linked organic polymers that form the residue described above. This fluorination typically increases chemical resistance. Thus, the residue becomes difficult, if not impossible, to remove by conventional wet stripping techniques. Ashing using an oxidative or reductive plasma can remove the residue. However, plasma ashing is prone to damage to the ILD materials, especially low-k ILD materials. [0006] Therefore, a need exists for photoresist removal that can remove photoresist residue but does not damage the ILD materials.
• ILD interlayer dielectric
• a wet-cleaning composition for removal of photoresist is provided.
• the composition comprises a strong base; an oxidant; and a polar solvent.
• a method for removing photoresist is provided. The method comprises the steps of (i) applying a wet-cleaning composition comprising about 0.1 to about 30 weight percent strong base, about one to about 30 weight percent oxidant, and about 20 to about 95 weight percent polar solvent; and (ii) removing the photoresist.
• a wet-cleaning composition for removal of photoresist includes a strong base.
• the strong base may yield a solution having a pH greater than about 11.5, even where the strong base makes up no more than about 3.5% of the solution. That is, the strong base may be no more than about 3.5 weight percent of the solution.
• higher strong base concentrations may be desirable.
• the strong base assists in the removal of the photoresist, e.g., unexposed positive photoresist.
• the composition also includes an oxidant and a polar solvent. Strong bases of the formula I, shown below, may be used in accordance with the teachings of the present invention.
• R j wherein R 1 , R 2 , R 3 and R 4 are each one of hydrogen, alkyl or substituted alkyl groups.
• Suitable strong bases include, but are not limited to, ammonium hydroxide, tetramethylammonium hydroxide (TMAH), choline hydroxide, as well as combinations comprising at least one of the foregoing strong bases.
• the strong base comprises tetramethylammonium hydroxide.
• the cleaning compostion or solution described is particularly useful for cleaning photoresist residue from a semiconductor substrate.
• a semiconductor substrate is patterned to form trenches therein. This is done in a manner employing a photoresist.
• the photoresist and any residue may be removed from the trench and substrate with the described cleaning solution.
• a semiconductor feature such as a metal line may be formed in the trench followed by chemical mechanical planarazation to isolate the metal line. Further semiconductor processing may follow to form a completed semiconductor device.
• the composition of the present invention comprises greater than or equal to about 0.1 weight percent strong base, with greater than or equal to about one weight percent strong base preferred and greater than or equal to about five weight percent strong base more preferred. In the exemplary embodiment, the composition of the present invention further comprises less than or equal to about 30 weight percent strong base, with less than or equal to about 20 weight percent strong base preferred and less than or equal to about ten weight percent strong base more preferred. [0012] The composition further comprises an oxidant.
• Suitable oxidants include, but are not limited to, inorganic oxidizers, organic oxidizers, e.g., amine-N-oxides, perborate salts, persulfate salts, percarbonate salts, as well as combinations comprising at least one of the foregoing oxidants.
• the oxidant comprises organic oxidizers.
• Organic oxidizers of the general formula II, shown below, may be used in accordance with the teachings of the present invention.
• R 1 , R 2 and R 3 may be hydrogen, methyl or further substituted or unsubstituted alkyl groups.
• R 1 and R 2 may form two ends of an alkyl chain.
• hile peroxides e.g., hydrogen peroxide and substituted alkyl or aryl peroxides
• amine-N-oxides have the advantage of being a more mild oxidant as compared to the peroxides in general. Further, amine-N-oxides decompose less rapidly as compared to peroxides in general.
• hydrogen peroxide in alkaline environments decomposes rapidly, yielding oxygen and water, a condition that leads to a short bath life especially at temperatures greater than ambient.
• hydrogen peroxide may be unstable in the presence of oxidizable organic species, for example, amines and alcohols.
• the composition of the present invention comprises greater than or equal to about one weight percent oxidant, with greater than or equal to about five weight percent oxidant preferred and greater than or equal to about ten weight percent oxidant more preferred.
• the composition of the present invention further comprises less than or equal to about 30 weight percent oxidant, with less than or equal to about 20 weight percent oxidant preferred and less than or equal to about 15 weight percent oxidant more preferred.
• the composition further comprises a polar solvent.
• the polar solvent solubilizes ionic components both in the photoresist and in the photoresist residues.
• Suitable polar solvent include, but are not limited to, water, ethylene, propylene, other glycol solvents, glycol ethers, alcohols, amides, carbonates, as well as combinations comprising at least one of the foregoing polar solvents.
• the polar solvent comprises water due to its low cost and non-toxicity.
• the composition of the present invention comprises greater than or equal to about 20 weight percent polar solvent, with greater than or equal to about 30 weight percent polar solvent preferred and greater than or equal to about 40 weight percent polar solvent more preferred. In the exemplary embodiment, the composition of the present invention further comprises less than or equal to about 95 weight percent polar solvent, with less than or equal to about 85 weight percent polar solvent preferred and less than or equal to about 75 weight percent polar solvent more preferred.
• the composition may further comprise a chelator.
• Suitable chelators include, but are not limited to, unsubstituted triazoles, substituted triazoles, thiazoles, tetrazoles, imidazoles, phosphates, thiols and azines, glycerols, amino acids, carboxylic acids, alcohols, amides, quinolines, as well as combinations comprising at least one of the foregoing chelators.
• Unsubstituted triazoles include, but are not limited to, 1,2,3-triazole and 1,2,4- triazole. Further, triazoles may be substituted with alkyl groups, amino groups, benzo groups, thiol groups, mercapto groups, i ino groups, carboxy groups, nitro groups, as well as combinations comprising at least one of the foregoing substituted groups.
• Substituted triazoles include, but are not limited to benzotriazole, polyltriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, l-amino-l,2,3-triazole, 1 -amino- 1,2,4-triazole, l-amino-5-methyl- 1,2,3-triazole, hydroxybenzotriazole,2-(5-amino-pentyl)-benzotriazole, 3-amino- 1,2,4- triazole,3-isopropyl-l ,2,4-triazole, 3-mercapto-l ,2,4-triazole, 5-phenylthiol-benzotriazole, halo-benzotriazoles, napthotriazole.
• Thiazoles, tetrazoles, imidazoles, phosphates, thiols and azines include, but are not limited to, 2-mercaptobenzoimidizole, 2- mercaptobenzothiazole, 5-aminotetrazole, 5-amino-l,3,4-thiadiazole-2-thiol, thiazole, triazine, methyltetrazole, l,3-dimethyl-2-imidazolidinone, 1,5-pentamethylenetetrazole, 1- phenyl-5-mercaptotetrazole, diaminomethyltriazine, mercaptobenzothiazole, imidazoline thione, mercaptobenzoimidazole, 4-methyl-4H-l,2,4-triazole-3 -thiol, benzothiazole, tritolyl phosphate, indiazole, as well as combinations comprising at least one of the foregoing.
• Glycerols amino acids, carboxylic acids, alcohols, amides, quinolines include, but are not limited to, guanine, adenine, glycerol, thioglycerol, nitrilotriacetic acid, salicylamide, iminodiacetic acid, benzoguanamine, melamine, thiocyranuric acid, anthranilic acid, 8- hydroxyquinoline, 5-carboxylic acid-benzotriazole, 3-mercaptopropanol, boric acid and iminodiacetic acid.
• the chelator may be added to the composition to prevent the etching or corrosion of metal surfaces, e.g., copper, tungsten, aluminum and alloys thereof, exposed to the composition. As such, the chelator may be used to increase the compatibility of the composition with the metals and dielectric materials used in the semiconductor device.
• the composition of the present invention comprises less than or equal to about ten weight percent chelator, with less than or equal to about seven weight percent chelator preferred and less than or equal to about four weight percent chelator more preferred.
• the composition may further comprise a co-solvent.
• the co-solvent may be added to improve compositional properties, namely the ability of the composition to swell, dissolve, and lift off photoresist residues.
• Suitable co-solvents include, but are not limited to, substituted alkylamines or alkanolamines such as N,N-dimethyldiglycolamine, 1,8- diazabicyclo[5.4.0]undecene, aminopropylmo holine, triethanolamine, methylethanolamine, glycol solvents such as ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, glycol ethers such as di(ethylene glycol)monoethyl ether, di(propylene glycol)propyl ether, ethylene glycol phenyl ether, di(propylene glycol) butyl ether, butyl carbitol, polyglycol ethers, as well as combinations comprising at least one of the for
• the co-solvent should be polar.
• a polar compound will remain miscible with the polar solvent and will keep ionic species such as tetramethylammonium hydroxide dissolved.
• the composition of the present invention comprises less than or equal to about 50 weight percent co-solvent, with less than or equal to about 30 weight percent co-solvent preferred and less than or equal to about 20 weight percent co-solvent more preferred.
• the composition may further comprise a surfactant.
• the surfactant may be added in order to assist in both the lifting-off of insoluble photoresist residues and reduce silicon etching, which may occur under exposure to strong bases.
• Suitable surfactants include, but are not limited to, anionic, cationic, nonionic surfactants, such as fluoroalkyl surfactants, polyethylene glycols, polypropylene glycols, polyethylene or polypropylene glycol ethers, carboxylic acid salts, dodecylbenzenesulfonic acid or salts thereof, polyacrylate polymers, silicone or modified silicone polymers, acetylenic diols or modified acetylenic diols, alkylammonium or modified alkylammonium salts, as well as combinations comprising at least one of the foregoing surfactants.
• the composition of the present invention comprises less than or equal to about 20 weight percent surfactant, with less than or equal to about 15 weight percent surfactant preferred and less than or equal to about ten weight percent surfactant more preferred.
• Another aspect of the invention provides a method for removing photoresist.
• the method comprises the steps of applying a wet-cleaning composition comprising about 0.1 to about 30 weight percent strong base; about one to about 30 weight percent oxidant; and about 20 to about 95 weight percent polar solvent; and removing the photoresist.
• a wet-cleaning composition comprising about 0.1 to about 30 weight percent strong base; about one to about 30 weight percent oxidant; and about 20 to about 95 weight percent polar solvent; and removing the photoresist.
• the term photoresist as used herein is generally applicable to any layer comprising photoresist.
• the composition and method herein may be used to remove photoresist as well as photoresist residue.
• teachings of the present invention apply to the removal of any photoresist residue, i.e., resulting from an etching process including, but not limited to, fluorine-based plasma etching.
• EXAMPLES [0028] The following formulations produced substantial cleaning of photoresist from a semiconductor substrate. Substantial cleaning, according to the teachings of the present invention, is defined as being greater than 80 percent removal of the photoresist from the semiconductor device, and may be determined by optical and electron microscopy.
• the substrate employed herein consisted of chemically amplified photoresist coated onto an organosilicate dielectric coated silicon wafer. Additionally, the photoresist was exposed to patterned radiation and developed, and the pattern was then transferred to the dielectric by a plasma etch.
• Composition A was prepared as follows:
• N-methylmorpholine-N-oxide was supplied and used as a 50 weight percent solution
• tetramethylammonium hydroxide (TMAH) was supplied and used as a 25 weight percent solution in the present example, as well as in further examples employing N- methylmorpholine-N-oxide and tetramethylammonium hydroxide (TMAH).
• TMAH tetramethylammonium hydroxide
• a photoresist substrate was cleaned by immersion in composition A for 20 minutes at 70°C. All of the photoresist and etch residues were removed from the substrates as observed by optical and electron microscopy. Significant etching of the dielectric material was not observed.
• compositions B, C and D were prepared, each containing 13.5 weight percent N- Methylmorpholine-N-oxide, 7.3 weight percent TMAH, 78.9 weight percent water and 0.3 weight percent of the inhibitor 2-mercaptobenzimidazole (2-MBI) as shown below.
• 2-MBI was included in the formulation in order to retard etching of copper or other metals by the solution, as may be seen in Example 3.
• Photoresist substrates were cleaned by immersion in the stripper for 20 minutes at 70°C.
• Etch rates of a blanket coating of copper (Cu) on a silicon wafer were measured using compositions A through D, as prepared above.
• the copper layer was deposited by physical vapor deposition and was about 1000 angstroms (A) in thickness. Samples were immersed in the composition for a fixed time, and the thickness was measured both before and after using four-point probe electrical measurements. Etch rates were calculated by dividing the difference in thickness, i.e., the thickness before etching, less the thickness after etching, by the time in minutes.
• the etch rates for compositions A through D are given below.
• Composition E was prepared as follows:
• Polyethyleneglycol 4-nonylphenyl ether is a surfactant containing about 5 ethyleneglycol
• Composition F was prepared as follows:
• compositions A and F were determined by immersing 1000 A wafer sections of polysilicon on silicon, in each composition, for 15 minutes at 70°C.
• Composition F showed no observable etching or roughening of the polysilicon surface.
• Composition A did show slight observable roughening of the polysilicon surface.
• Composition G was prepared as follows:
• a photoresist substrate was cleaned by immersion in composition G for 20 minutes at 70°C. All of the photoresist and etch residues were removed from the substrates, as observed by optical and electron microscopy. However, etching or roughening of polysilicon was observed under the same conditions.
• Composition H was prepared as follows:
• Composition I was prepared as follows:
• composition I showed removal of the photoresist with moderate protection of the polysilicon. Some etching or roughening was exhibited when the polysilicon was immersed in the sample for 15 minutes at 70°C. The copper etch rate remained low at 0.15 A /minute and the tungsten etch rate was 0.67 A /minute. The copper and tungsten samples were immersed for 40 minutes at 70°C.
• Composition J was prepared as follows:
• Composition J resulted in complete removal of photoresist and residues from the trench features and about 40 percent photoresist residue removal from the bond pad area.
• the trench features consisted of 1:1 line/space pairs of about 0.2 micron dimension
• the bond pad areas consisted of a square array of square dummy features of about 2 microns dimension.
• Composition K was prepared as follows:
• Composition K resulted in some residual photoresist on the trench features with five percent of the bond pad area cleaned with immersion in composition K for 20 minutes at 70°C.
• Composition L was prepared as follows:
• Composition L resulted in complete photoresist removal from the trench features and greater than 99.9 percent removal from the bond pad area when immersed for 16 minutes at 70°C.
• Composition M was prepared as follows:
• Composition M resulted in ten percent photoresist removal in the trench features and zero percent in the bond pad area when immersed for 16 minutes at 70°C.
• Composition N was prepared as follows:
• Composition N resulted in complete photoresist crust removal from the trench features and 95 percent photoresist removal from the bond pad areas when immersed for 20 minutes at 70°C.
• Composition O was prepared as follows:
• Polyethyleneglycol dinonylphenyl ether is a surfactant containing about 150 ethyleneglycol repeat units.
• Composition O resulted in complete photoresist crust removal from the trench features and complete percent photoresist removal from the bond pad areas when immersed for 20 minutes at 70°C.
• Comparative composition I consisted of ten weight percent hydroxylamine, ten weight percent water and 80 weight percent diglycolamine. Etched photoresist substrates were immersed in the composition for 30, 50 and 60 minutes at 70°C, followed by a rinsing with water. Inspection by optical and electron microscopy revealed that comparative composition I dissolved photoresist from under the top layer of photoresist residue, but left the layer of residue collapsed and attached to the samples in all regions.

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• 2003
  • 2003-03-14 US US10/389,214 patent/US8236485B2/en not_active Expired - Lifetime
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