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
  • G03F7/34—Imagewise removal by selective transfer, e.g. peeling away
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02041—Cleaning
  • H01L21/02057—Cleaning during device manufacture
  • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
  • H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K13/00—Etching, surface-brightening or pickling compositions
  • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
  • C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
• • 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
• • 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
• • 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
• • 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

• This invention relates to methods and post-etch and/or photoresist ash residue cleaning compositions for cleaning microelectronics substrates, particularly aluminum or titanium containing microelectronic components.
• the compositions of this invention provide enhanced protection of metal, i.e., inhibition of corrosion, when such microelectronic substrates are subjected to cleaning and a subsequent aqueous rinse.
• the resist mask must be removed from the protected area of the substrate so that the next process operation can take place. This can be accomplished in a plasma ashing step by the use of suitable plasma ashing gases or wet chemical strippers. Finding a suitable cleaning composition for removal of this resist mask material without adversely affecting, e.g., corroding, etching or dulling, the metal circuitry has also proven problematic.
• a plasma ashing step by the use of suitable plasma ashing gases or wet chemical strippers.
• Finding a suitable cleaning composition for removal of this resist mask material without adversely affecting, e.g., corroding, etching or dulling, the metal circuitry has also proven problematic.
• FPD semiconductors and flat panel displays
• a typical residue remover for microelectronic applications might be an alkaline- containing composition that includes polar organic solvents blended with organic amines or hydroxylamines or other strong bases typically in polar organic solvents and other solvating agents in an attempt to lessen metal and dielectric attack or corrosion.
• Amines, hydroxylamines and other strong bases have been shown to increase the effectiveness of photoresist and residue removal in solvent blends.
• alkaline ash residue removal formulations experience carbon dioxide uptake from the air, which in most cases shortens the cleaner solution's effective bath life.
• these alkaline cleaner compositions are relatively slow acting and require the substrates to be kept in the cleaner solutions for extended times at elevated temperatures.
• the water rinse following this type of remover can create a strongly alkaline aqueous solution and that can lead to considerable loss of metal from the patterned lines, particularly aluminum which is very sensitive to corrosion in alkaline aqueous solution.
• Such an intermediate rinse typically with isopropyl alcohol, adds undesirable time, safety concerns, environmental consequences, and cost to the manufacturing process.
• the invention provides cleaning compositions for cleaning microelectronic substrates that are able to essentially completely clean such substrates and inhibit metal corrosion or produce essentially no corrosion of the metal elements of such substrates, and to do so at relatively short cleaning times and relatively low temperatures compared to the cleaning times required for prior art alkaline-containing cleaning compositions.
• the invention also provides method of using such cleaning compositions to clean microelectronic substrates without producing any significant corrosion of the metal elements of the microelectronic substrate.
• the cleaning compositions of this invention comprise
• the cleaning compositions of this invention optionally can have present in the compositions other components, such as for example surfactants, metal complexing or chelating agents, corrosion inhibitors, and the like.
• the cleaning compositions of this invention are characterized by an absence of organic amines, hydroxylamines or other strong bases such as ammonium bases and the like that would neutralize the inorganic phosphorus-containing acid component.
• the cleaning and residue removal compositions of this invention are especially suitable for cleaning microelectronic substrates containing aluminum, titanium, and tungsten.
• the invention provides cleaning compositions for cleaning microelectronic substrates that are able to essentially completely clean such substrates and inhibit metal corrosion or produce essentially no corrosion of the metal elements of such substrates.
• the invention also provides method of using such cleaning compositions to clean microelectronic substrates without producing any significant corrosion of the metal elements of the microelectronic substrate.
• the cleaning compositions of this invention comprise (a) at least one organic solvent, (b) at least one unneutralized inorganic phosphorus- containing acid, and (c) water.
• the cleaning compositions of this invention contain one or more suitable water- soluble or water miscible organic solvents.
• suitable organic solvents suitable are alcohols, polyhydroxy alcohols, such as for example, glycerol, glycols, such as for example propylene glycol and diethylene glycol, glycol ethers, such as for example 2-(2-ethoxyethoxy)ethanol (carbitol), alkyl- pyrrolidinones, such as for example N-methylpyrrolidinone (NMP), 1-hydroxyalkyl-2-pyrrolidinones such as for example, 1-(2-hydroxyethyl)-2-pyrrolidinone (HEP), dimethylformamide (DMF), dimethylacetamide (DMAC), sulfones, such as for example sulfolane, and sulfoxides, such as for example, dimethylsulfoxide (DMSO).
• alcohols such as for example, glycerol
• glycols such as for example propylene glycol and diethylene glycol
• the organic solvents are preferably polar organic solvents.
• Preferred water-soluble organic solvents are diethylene glycol, propylene glycol, N-methylpyrrolidinone, sulfolane, DMSO and dimethylacetamide.
• the cleaning compositions of this invention contains one or more organic solvent generally in an amount of from about 35% to about 95%, preferably from about 60% to about 90%, more preferably from about 75% to about 85%, by weight of the composition.
• the cleaning compositions of this invention contain one or more unneutralized inorganic-phosphorus-containing acid.
• Any suitable unneutralized inorganic phosphorus-containing acid may be employed in the cleaning compositions of this invention.
• Examples of such unneutralized inorganic-phosphorus-containing acid include, but are not limited to, phosphorous (H 3 PO 3 ), hypophosphorous (H 3 PO 2 ) and phosphoric acids (H 3 PO 4 ).
• the unneutralized inorganic-phosphorus- containing acid component of the cleaning composition will be present in the cleaning composition in an amount such that the weight ratio of the organic solvent component to the unneutralized inorganic- phosphorus-containing acid component is from about 3:1 to about 40:1 , preferably from about 3:1 to about 20:1 and more preferably from about 4:1 to about 10:1
• the water component of the cleaning composition of this invention may be present in an amount of from about 3% to about 60%, preferably from about 5% to about 50%, and more preferably from about 5% to about 10%, by weight of the composition.
• the water component will be added to the cleaning composition as part of the unneutralized inorganic phosphorus-containing acid component since such acids are normally available as water-containing solutions.
• the water may however be added as a separate component apart from or in addition to the acid component.
• compositions of the present invention may also contain any suitable water-soluble amphoteric, non-ionic, cationic or anionic surfactant.
• a surfactant will reduce the surface tension of the formulation and improve the wetting of the surface to be cleaned and therefore improve the cleaning action of the composition.
• the surfactant may also be added to reduce aluminum corrosion rates if further aluminum corrosion inhibition is desired. Further, surfactant properties may aid the dispersion of particulates, facilitating better cleaning. Any suitable amphoteric, cationic or non-ionic surfactant may be employed in the compositions of this invention.
• surfactants include, but are not limited to 3,5-dimethyl-1-hexyn-3-ol (Surfynol-61), ethoxylated 2,4,7,9- tetramethyl-5-decyne-4,7-diol (Surfynol-465), polytetrafluoroethylene cetoxypropylbetaine (Zonyl FSK), Zonyl FSH, Triton X-100, namely octylphenoxypolyethoxyethanol, and the like.
• the surfactant will generally be present in an amount of from 0 to about 5 wt%, preferably 0.001 to about 3 wt% based on the weight of the composition.
• the cleaning compositions of this invention can also optionally contain other components, including but not limited to, corrosion inhibitors and similar non-corrosive components employed in microelectronic cleaning compositions.
• the compounds may include catechol, resorcinol, gallic acid, propyl gallate, pyrogallol, hydroquinone, derivatives of benzotriazole, and polyfunctional carboxylic acids such as citric acid, tartaric acid, gluconic acid, saccharic acid, glyceric acid, oxalic acid, phthalic acid, maleic acid, mandelic acid, malonic acid, lactic acid, and salicylic acid.
• Organic or inorganic chelating or metal complexing agents are not required, but may offer substantial benefits, such as for example, improved product stability, cleaning, and corrosion prevention when incorporated into the cleaning compositions of this invention.
• suitable chelating or complexing agents include but are not limited to trans-1 ,2-cyclohexanediamine tetraacetic acid (CyDTA), ethylenediamine tetraacetic acid (EDTA), pyrophosphates, alkylidene-diphosphonic acid derivatives (e.g. 1- hydroxyethane-1 ,1-diphosphonate (HEDPA)).
• the chelating agent will be present in the composition in an amount of from 0 to about 5 wt%, preferably from about 0.1 to about 2 wt% based on the weight of the composition.
• the cleaning composition comprises hypophosphorous acid and water along with one or more of N-methylpyrrolidinone, sulfolane, diethylene glycol, and DMSO.
• the cleaning composition comprises phosphorous acid and water along with one or more of N-methylpyrrolidinone, sulfolane, diethylene glycol, and DMSO.
• the invention comprises a method of cleaning a microelectronic substrate, the substrate containing photoresist polymeric material, residues, such as ashing or etching residues, and metal containing layers, the method comprising contacting the substrate with a cleaning composition for a time sufficient to clean the substrate, wherein the cleaning composition comprises the following components: a. at least one water-soluble or water-miscible organic solvent, b. at least one unneutralized inorganic phosphorus-containing acid, and c. water, wherein the composition is free of organic amines, hydroxylamines and strong bases that would neutralize the inorganic phosphorus-containing acid component.
• the method is especially suitable for cleaning microelectronic substrates containing multiple metal layers and particularly substrates characterized by the presence of aluminum, titanium and tungsten metals.
• the compositions of this invention, their use to clean microelectronic substrates and their non-metal corroding properties is illustrated by, but not limited to, the following examples. [0018] In the following Examples and Tables the following abbreviation are employed.
• HPA hypophosphorous acid
• PA phosphorous acid
• HEDPA 1-hydroxyethane-1 ,1-diphosphonic acid
• compositions of this invention were tested for their ability to clean microelectronic devices by immersing in the compositions of this invention substrates having AI/TiN (aluminum/titanium nitride) layers that had been coated with photoresist, exposed, developed, hard etched and ashed to produce titanium rich vias that are generally very difficult to clean at low temperatures.
• the sample substrates were immersed in the cleaning compositions at 45 0 C for 10 minutes, followed by a 1 min. Dl water rinse.
• Table 1 demonstrate the cleaning and relatively non-corrosive nature of the composition of this invention.
• compositions of this invention were tested for their ability to clean microelectronic devices by immersing in the compositions of this invention substrates having AI/TiN layers that had been coated with photoresist, exposed, developed, hard etched and ashed to produce metal lines that are generally more easy to clean than the vias in Examples 1-7.
• the sample substrates were immersed in the compositions at 65 0 C for 20 minutes, followed by a 1 min. Dl water rinse.
• the results in Table 2 demonstrate the cleaning and relatively non-corrosive nature of the composition of this invention, particularly in the presence of select additives. Table 2

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• General Physics & Mathematics (AREA)
• Physics & Mathematics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Wood Science & Technology (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Life Sciences & Earth Sciences (AREA)
• Inorganic Chemistry (AREA)
• Computer Hardware Design (AREA)
• Manufacturing & Machinery (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Power Engineering (AREA)
• Materials Engineering (AREA)
• Detergent Compositions (AREA)
• Cleaning Or Drying Semiconductors (AREA)
• Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

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• 2006
  • 2006-04-18 KR KR1020077025627A patent/KR20080005408A/ko not_active Ceased
  • 2006-04-18 EP EP06750494.4A patent/EP1883863B1/en not_active Not-in-force
  • 2006-04-18 WO PCT/US2006/014466 patent/WO2006121580A2/en not_active Ceased
  • 2006-04-18 US US11/911,346 patent/US7754668B2/en not_active Expired - Fee Related
  • 2006-04-18 JP JP2008510018A patent/JP2008541426A/ja active Pending
  • 2006-04-18 BR BRPI0611377-0A patent/BRPI0611377A2/pt not_active IP Right Cessation
  • 2006-04-18 CA CA002606849A patent/CA2606849A1/en not_active Abandoned
  • 2006-04-18 CN CN2006800155059A patent/CN101171551B/zh active Active
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• 2007
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