WO2005085957A1 - Composition and process for post-etch removal of photoresist and/or sacrificial anti-reflective material deposited on a substrate - Google Patents

Composition and process for post-etch removal of photoresist and/or sacrificial anti-reflective material deposited on a substrate Download PDF

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Publication number
WO2005085957A1
WO2005085957A1 PCT/US2005/006713 US2005006713W WO2005085957A1 WO 2005085957 A1 WO2005085957 A1 WO 2005085957A1 US 2005006713 W US2005006713 W US 2005006713W WO 2005085957 A1 WO2005085957 A1 WO 2005085957A1
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aqueous solution
formulation
water
hydroxide
weight
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PCT/US2005/006713
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English (en)
French (fr)
Inventor
Melissa K. Rath
David D. Bernhard
David Minsek
Michael B. Korzenski
Thomas H. Baum
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Advanced Technology Materials Inc
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Advanced Technology Materials Inc
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Priority to CA002599727A priority Critical patent/CA2599727A1/en
Priority to EP05724288.5A priority patent/EP1730600B1/en
Priority to JP2007501931A priority patent/JP4758982B2/ja
Priority to KR1020067020256A priority patent/KR101256230B1/ko
Priority to CN2005800105407A priority patent/CN1938647B/zh
Publication of WO2005085957A1 publication Critical patent/WO2005085957A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/435—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom
    • A61K31/44—Non condensed pyridines; Hydrogenated derivatives thereof
    • 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
    • C11D1/38—Cationic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium 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
    • 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
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/06—Hydroxides
    • 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
    • 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 and process useful for removal of post-etch photoresist and or sacrificial anti-reflective coating material from a substrate or article having such material deposited thereon.
  • SARC materials are based on tetraethylorthosilicate (TEOS), ( they are etchable in a similar manner and at similar rate to SiOC-based dielectric material. This allows a very high level of etch uniformity and etch control to be achieved, to such extent that trench etch stop layers are not required, and via etch stop layers can be reduced in thickness by up to 50%, in relation to the aforementioned alternative approaches.
  • etched SARCs can be removed by liquid cleaner/etchant compositions, since etched SARCs do not significantly increase their degree of cross-linking after etch, in relation to organic-based photoresists and BARCs.
  • Untreated photoresist possesses solubility in strong aqueous alkaline solutions as well as solutions of select organic solvents.
  • photoresist that has been exposed to gas-phase plasma etching such is typically used for etching of dielectric materials, will develop a hardened crust on the surface of the material.
  • the hardened crust is composed of cross-linked organic polymer and may contain small amounts of silicon or metal atoms.
  • Fluorine-based plasma etches as used in dual damascene processes may deposit fluorine atoms in the photoresist crust, which may decrease its solubility and increase its resistance to chemical removal.
  • the photoresist and crust can be removed by gas phase ashing where the substrate is exposed to an oxidative or reductive plasma etch, but these plasma ashing techniques can cause damage to the dielectric, especially porous, organosilicate or organic low k materials, causing an unacceptable increase in k value.
  • the semiconductor features of the structure being fabricated may contain metals vital to the operation of the eventual product chip, such as copper, aluminum and alloys of cobalt.
  • Hydroxylamine solutions have been utilized in the art for photoresist removal, but such solutions have associated corrosion, toxicity and reactivity problems that limit their use, with adverse corrosion effects being particularly problematic when copper is employed in the integrated circuitry.
  • the present invention in one aspect relates to a cleaning composition useful for removing photoresist and or sacrificial anti-reflective coating (SARC) materials from a substrate having such material(s) thereon.
  • the composition includes an active cleaning combination (ACC) selected from the group consisting of: (a) a quaternary ammonium base in combination with at least one of alkali and alkaline earth base; and (b) a strong base in combination with an oxidant.
  • ACC active cleaning combination
  • Another aspect of the invention relates to a method of removing photoresist and/or SARC material from a substrate having said material thereon, said method comprising contacting the substrate with a cleaning composition for sufficient time to at least partially remove said material from the substrate, wherein the cleaning composition includes an active cleaning combination (ACC) selected from the group consisting of: (a) a quaternary ammonium base in combination with at least one of alkali and alkaline earth base; and (b) a strong base in combination with an oxidant.
  • ACC active cleaning combination
  • the present invention contemplates cleaning compositions that are useful to remove photoresist and/or sacrificial anti-reflective coating (SARC) materials from a substrate having such material(s) thereon.
  • SARC photoresist and/or sacrificial anti-reflective coating
  • the composition includes an active cleaning combination (ACC) selected from the group consisting of: (a) a quaternary ammonium base in combination with at least one of alkali and alkaline earth base; and (b) a strong base in combination with an oxidant.
  • ACC active cleaning combination
  • compositions of the invention may be embodied in a wide variety of specific formulations, as hereinafter more fully described.
  • compositions wherein specific components of the composition are discussed in reference to weight percentage ranges including a zero lower limit, it will be understood that such components may be present or absent in various specific embodiments of the composition, and that in instances where such components are present, they may be present at concentrations as low as 0.01 weight percent, based on the total weight of the composition in which such components are employed.
  • the present invention in one aspect thereof relates to a cleaning composition useful for removal of SARCs and photoresist, which includes the following components:
  • organic quaternary ammonium base 0.01-5 weight % alkali or alkaline earth base 0-80 weight % solvent(s) and/or amine(s) 0-5 weight % surfactant 0 - 10 weight % chelator/passivation agent 0 - 98 weight % water
  • percentages of the components are percentages by weight, based on total weight of the composition, and wherein the total of the weight percentages of such components of the composition does not exceed 100 weight %.
  • composition may optionally include additional components, including active as well as inactive ingredients, e.g., stabilizers, dispersants, anti-oxidants, penetration agents, adjuvants, additives, fillers, excipients, etc.
  • active e.g., stabilizers, dispersants, anti-oxidants, penetration agents, adjuvants, additives, fillers, excipients, etc.
  • the composition may variously comprise, consist of, or consist essentially of, the aforementioned organic quaternary ammonium base, alkali or alkaline earth base, solvent(s) and/or amine(s), surfactant, chelator/passivation agent, and water components.
  • the cleaning composition includes the following components:
  • organic quaternary ammonium base ⁇ 0.01-2 weight % alkali or alkaline earth base 0-50 weight % solvent(s) and/or amine(s) -0.01-2 weight % surfactant 0 - 5 weight % chelator/passivation agent 40 - 95 weight % water wherein percentages of the components are percentages by weight, based on total weight of the composition, and wherein the total of the weight percentages of such components of the composition does not exceed 100 weight %.
  • the cleaning composition is formulated in the following Formulations A-G, wherein all percentages are by weight, based on the total weight of the formulation:
  • oxirane methyl-, polymer with oxirane, mono(octylphenyl)ether
  • the present invention relates to a cleaning composition that is useful for stripping photoresist and/or photoresist residues from semiconductor substrates and/or SARCs while maintaining cobalt and copper compatibility.
  • cleaning composition includes an aqueous solution of at least one oxidant, a strong base, optionally a chelator and optionally a co-solvent and/or a surfactant.
  • the cleaning composition effectively removes photoresist from the top of the semiconductor device without causing damage to the dielectric material and without causing corrosion of the underlying metal.
  • Compositions of such type in which the base component includes potassium hydroxide are especially advantageous in achieving high efficiency cleaning without adverse effect on the dielectric layer.
  • compositions of such type include the following components by weight, based on the total weight of the composition:
  • strong base means a cation/anion salt that dissociates in aqueous or partially aqueous solutions to yield virtually stoichiometric amounts of hydroxide anions.
  • the strong base can include bases such as potassium hydroxide and alkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH), choline hydroxide, benzyltrimethylammonium hydroxide, etc.
  • compositions of the invention are devoid of hydroxylamine.
  • the oxidant in such composition can include, without limitation, inorganic and/or organic oxidizers, such as hydrogen peroxide, organic peroxides, amine-N-oxides, perborate salts, persulfate salts, as well as combinations of two or more of the foregoing.
  • inorganic and/or organic oxidizers such as hydrogen peroxide, organic peroxides, amine-N-oxides, perborate salts, persulfate salts, as well as combinations of two or more of the foregoing.
  • the chelator in such composition can be of any suitable type, and may include, without limitation, triazoles, such as 1,2,4-triazole, or triazoles substituted with substituents such as C1-C8 alkyl, amino, thiol, mercapto, imino, carboxy and nitro groups, such as benzotriazole, tolyltriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, 3-amino-5- mercapto- 1,2,4-triazole, 1 -amino- 1,2,4-triazole, hydroxybenzotriazole, 2-(5-amino-pentyl)- benzotriazole, l-amino-l,2,3-triazole, l-amino-5-methyl-l,2,3-triazole, 3-amino- 1,2,4- triazole, 3 -mercapto- 1,2,4-triazole, 3-isopropyl- 1,2,4-triazole,
  • Suitable chelator species further include glycerols, amino acids, carboxylic acids, alcohols, amides and quinolines such as guanine, adenine, glycerol, thioglyceroL nitrilotriacetic acid, salicylamide, iminodiacetic acid, benzoguanamine, melamine, thiocyranuric acid, anthranilic acid, gallic acid; ascorbic acid; salicylic acid; 8- hydroxyquinoline, 5-carboxylic acid-benzotriazole, 3-mercaptopropanol, boric acid, iminodiacetic acid, etc.
  • the chelator is usefully employed to increase the compatibility of the composition with the metals and the dielectric materials used in the semiconductor device.
  • the surfactant employed in the composition can be of any suitable type, e.g., 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, dinonylphenyl polyoxyethylene, or other substituted phenyl polyoxyethylenes, silicone or modified silicone polymers, acetylenic diols or modified acetylenic diols, alkylammonium or modified alkylammonium salts, as well as combinations of two or more of the foregoing.
  • nonionic surfactants such as fluoroalkyl surfactants, polyethylene glycols, polypropylene glycols, polyethylene or polyprop
  • Suitable co-solvent species for such composition include, without limitation, amines such as dimethyldiglycolamine, l,8-diazabicyclo[5.4.0]undecene, aminopropylmorpholine, triethanolamine, methylethanolamine, methyldiethanolamine, etc. or glycols such as ethylene or polyethylene, propylene glycol, neopentyl glycol, etc., amines such as hydroxyethylmorpholine, aminopropylmo ⁇ holine, etc.
  • amines such as dimethyldiglycolamine, l,8-diazabicyclo[5.4.0]undecene, aminopropylmorpholine, triethanolamine, methylethanolamine, methyldiethanolamine, etc. or glycols such as ethylene or polyethylene, propylene glycol, neopentyl glycol, etc.
  • amines such as hydroxyethylmorpholine, aminopropylmo ⁇ holine, etc.
  • glycol ethers such as di(ethylene glycol)monoethyl ether, di(propylene glycoPjpropyl ether, ethylene glycol phenyl ether, di(propylene glycol) butyl ether, butyl carbitol, etc., or polyglycol ethers.
  • Formulations H-S Specific embodiments of such composition are set out as Formulations H-S below, wherein all percentages are by weight, based on the total weight of the composition.
  • N-mefhylmorpholine oxide 50% aqueous solution 7.0 % dinonylphenol polyoxyethylene, 7% aqueous solution 4.3 %
  • N-methylmorpholine oxide 50%> aqueous solution 7.0 % dinonylphenol polyoxyethylene, 7%> aqueous solution 4.3 %> ammonium tetrathiomolybdate 0.1 % water 73.9 %
  • N-methylmorpholine oxide 50% aqueous solution 7.0 % dinonylphenol polyoxyethylene, 7% aqueous solution 4.3 %
  • N-methylmorpholine oxide 50%
  • aqueous solution 7.0 % dinonylphenol polyoxyethylene 7%> aqueous solution 4.3 %>
  • N-methylmorpholine oxide 50% aqueous solution 7.0 % dinonylphenol polyoxyethylene, 7% aqueous solution 4.3 %>
  • N-methylmorpholine oxide 50% aqueous solution 7.0 %> dinonylphenol polyoxyethylene, 7% aqueous solution 4.3 %
  • N-methylmorpholine oxide 50% aqueous solution 7.0 % dinonylphenol polyoxyethylene, 7% aqueous solution 4.3 %
  • Formulation O tetramethylammonium hydroxide, 25% aqueous solution 14.7 % N-methylmorpholine oxide, 50% aqueous solution 7.0 % dinonylphenol polyoxyethylene, 7% aqueous solution 4.3 %
  • N-methylmorpholine oxide 50% aqueous solution 7.0 % dinonylphenol polyoxyethylene 7% aqueous solution 4.3 %
  • N-methylmorpholine oxide 50% aqueous solution 7.0 % dinonylphenol polyoxyethylene, 7% aqueous solution 4.3 %
  • Formulation R benzyltrimethylammonium hydroxide, 40% aqueous solution 9.0 % potassium hydroxide, 45% aqueous solution 0.6 %
  • N-methymiorpholine oxide 50% aqueous solution 7.0 % dinonylphenol polyoxyethylene, 7% aqueous solution 4.3 %
  • Formulation S benzyltrimethylammonium hydroxide, 40%> aqueous solution 9.0 % potassium hydroxide, 45% aqueous solution 0.6 %
  • N-methylmorpholine oxide 50% aqueous solution 7.0 % dinonylphenol polyoxyethylene, 7%> aqueous solution 4.3 %>
  • the invention contemplates cleaning compositions that include the following components by weight, based on the total weight of the composition:
  • the strong base, oxidant, chelator, co-solvent and surfactant species in such composition may be of same or corresponding species to those discussed illustratively hereinabove.
  • compositions are set out as Formulations T, U, V, W, X, Y, Z, A 2 , B 2 , C 2 , D 2 , E 2 , F 2 , G 2 , H 2 , 1 2 , J 2 , K 2 and L 2 below, wherein all percentages are by weight, based on the total weight of the composition.
  • N-methylmorpholine oxide 50% aqueous solution 7.0 %
  • N-methylmorpholine oxide 50% aqueous solution 7.0 %
  • N-methylmo ⁇ holine oxide 50% aqueous solution 7.0 %
  • N-methylmorpholine oxide 50% aqueous solution 7.0 %
  • N-methylmo ⁇ holine oxide 50% aqueous solution 7.0 %
  • N-methylmo ⁇ holine oxide 50% aqueous solution 7.0 %
  • Formulation A 2 benzyltrimethylammonium hydroxide, 40% aqueous solution 7.2 %
  • N-methylmo ⁇ holine oxide 50% aqueous solution 7.0 %
  • Formulation B benzyltrimethylammonium hydroxide, 40% aqueous solution 22.26 % Potassium hydroxide, 45% aqueous solution 0.6 %
  • Formulation D 2 benzyltrimethylammonium hydroxide, 40% aqueous solution 22.26 %
  • Formulation F 2 benzyltrimethylammonium hydroxide, 40% aqueous solution 22.26 %
  • Formulation I 2 benzyltrimethylammonium hydroxide, 40%> aqueous solution 22.26 %>
  • Formulation K 2 benzyltrimethylammonium hydroxide, 40% aqueous solution 7.2 %
  • Formulation L 2 benzyltrimethylammonium hydroxide, 40% aqueous solution 7.2 %
  • formulations within the broad scope of the present invention which are suitable for stripping photoresist and/or photoresist residues from semiconductor substrates, while maintaining cobalt and copper compatibility, include the formulations M 2 , N 2 , O 2 , P 2 , Q 2 and R 2 whose compositions are set out below.
  • Formulation M 2 tetramethylammonium hydroxide, 25% aqueous solution 4.0 % hydrogen peroxide, 30% aqueous solution 2.0 %
  • Formulation O tetramethylammonium hydroxide, 25% aqueous solution 4.0 % hydrogen peroxide, 30% aqueous solution 2.0 %
  • Formulation P 2 tetramethylammonium hydroxide, 25% aqueous solution 4.0 % hydrogen peroxide, 30% aqueous solution 2.0 %
  • Formulation Q 2 tetramethylammonium hydroxide, 25% aqueous solution 4.0 % hydrogen peroxide, 30% aqueous solution 2.0 %
  • Formulation R 2 tetramethylammonium hydroxide, 25% aqueous solution 4.0 % hydrogen peroxide, 30%> aqueous solution 2.0 %
  • the cleaning compositions of the invention are easily formulated by simple addition of the respective ingredients and mixing to homogeneous condition.
  • the cleaning composition is applied in any suitable manner to the material to be cleaned, e.g., by spraying the cleaning composition on the surface of the material to be cleaned, by dipping (in a volume of the cleaning composition) of the material or article including the material to be cleaned, by contacting the material or article to be cleaned with another material, e.g., a pad, or fibrous sorbent applicator element, that is saturated with the cleaning composition, or by any other suitable means, manner or technique, by which the cleaning composition is brought into cleaning contact with material to be cleaned.
  • the cleaning compositions of the present invention are usefully employed to remove photoresist and/or SARC materials from substrates and semiconductor device structures on which such material(s) have been deposited.
  • compositions of the present invention by virtue of their selectivity for such photoresist and/or SARC materials, relative to other materials that may be present on the semiconductor substrate and exposed to the cleaning composition, such as ILD structures, metallization, barrier layers, etc., achieve removal of the photoresist and/or SARC material(s) in a highly efficient manner.
  • the cleaning composition typically is contacted with the substrate for a time of from about 10 to about 45 minutes, at temperature in a range of from about 50°C to about 80°C.
  • Such contacting times and temperatures are illustrative, and any other suitable time and temperature conditions may be employed that are efficacious to at least partially remove the photoresist and/or SARC material from the substrate, within the broad practice of the invention.
  • the cleaning composition is readily removed from the substrate or article to which it has previously been applied, e.g., by rinse, wash, or other removal ste ⁇ (s), as may be desired and efficacious in a given end use application of the compositions of the present invention.
  • the substrate was a post-etch structure on a silicon wafer containing patterned organosilicate dielectric and SARC structures underneath patterned photoresist.
  • the photoresist was a standard commercially available chemically amplified resist for 193 or 248 nm lithography. Substantial cleaning is defined as greater than 80% removal of the photoresist from the semiconductor device, as determined by optical microscopy.
  • compositions of the invention are useful for removal of photoresist and/or SARCs from semiconductor substrates having same coated thereon. Further, such compositions can be employed without adverse effect on metallization on the substrate, e.g., copper, aluminum and cobalt alloys.
  • the cleaning compositions of the invention are readily formulated with suitable solvent systems, e.g., aqueous and semi-aqueous solvent systems, conferring low toxicity and low combustibility characteristics to such compositions.
  • suitable solvent systems e.g., aqueous and semi-aqueous solvent systems
  • the cleaning compositions of the present invention achieve a substantial advance in the art of removing photoresist and/or SARC materials, in the manufacture of integrated circuit devices.

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PCT/US2005/006713 2004-03-03 2005-03-02 Composition and process for post-etch removal of photoresist and/or sacrificial anti-reflective material deposited on a substrate Ceased WO2005085957A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA002599727A CA2599727A1 (en) 2004-03-03 2005-03-02 Composition and process for post-etch removal of photoresist and/or sacrificial anti-reflective material deposited on a substrate
EP05724288.5A EP1730600B1 (en) 2004-03-03 2005-03-02 Composition and process for post-etch removal of photoresist and/or sacrificial anti-reflective material deposited on a substrate
JP2007501931A JP4758982B2 (ja) 2004-03-03 2005-03-02 基板上に付着したフォトレジスト及び／又は犠牲反射防止材料のエッチング後除去のための組成物並びにプロセス
KR1020067020256A KR101256230B1 (ko) 2004-03-03 2005-03-02 기판에 증착된 포토레지스트 및/또는 희생 반사―방지성물질의 포스트―에치 제거를 위한 조성물 및 공정
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US8338087B2 (en) 2012-12-25
TW200534364A (en) 2005-10-16
EP1730600A1 (en) 2006-12-13
CN1938647B (zh) 2012-08-29
CN1938647A (zh) 2007-03-28
TWI408728B (zh) 2013-09-11
KR101256230B1 (ko) 2013-04-17
KR20070017509A (ko) 2007-02-12
EP1730600A4 (en) 2010-07-28
JP2007526523A (ja) 2007-09-13
US20050197265A1 (en) 2005-09-08
JP4758982B2 (ja) 2011-08-31
EP1730600B1 (en) 2016-01-06
CA2599727A1 (en) 2005-09-15
US20130109605A1 (en) 2013-05-02

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