WO2003006599A1 - Microelectronic cleaning compositions containing ammonia-free fluoride salts - Google Patents

Microelectronic cleaning compositions containing ammonia-free fluoride salts Download PDF

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Publication number
WO2003006599A1
WO2003006599A1 PCT/US2002/021436 US0221436W WO03006599A1 WO 2003006599 A1 WO2003006599 A1 WO 2003006599A1 US 0221436 W US0221436 W US 0221436W WO 03006599 A1 WO03006599 A1 WO 03006599A1
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WO
WIPO (PCT)
Prior art keywords
atoms
group
weight
cleaning composition
hydroxyethyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2002/021436
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English (en)
French (fr)
Inventor
Chin-Pin Sherman Hsu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Avantor Performance Materials LLC
Original Assignee
Mallinckrodt Baker Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to DE60238258T priority Critical patent/DE60238258D1/de
Priority to BR0210895-0A priority patent/BR0210895A/pt
Priority to AU2002316588A priority patent/AU2002316588A1/en
Priority to IL15976002A priority patent/IL159760A0/xx
Priority to KR1020047000267A priority patent/KR101031926B1/ko
Priority to YU1004A priority patent/RS51684B/sr
Priority to DK02746902.2T priority patent/DK1404795T3/da
Priority to CA2452921A priority patent/CA2452921C/en
Priority to EP02746902A priority patent/EP1404795B1/en
Priority to US10/483,036 priority patent/US7247208B2/en
Priority to PL368044A priority patent/PL199393B1/pl
Priority to JP2003512358A priority patent/JP4188232B2/ja
Application filed by Mallinckrodt Baker Inc filed Critical Mallinckrodt Baker Inc
Priority to AT02746902T priority patent/ATE487785T1/de
Publication of WO2003006599A1 publication Critical patent/WO2003006599A1/en
Priority to IL159760A priority patent/IL159760A/en
Priority to NO20040070A priority patent/NO20040070L/no
Anticipated expiration legal-status Critical
Priority to US11/762,087 priority patent/US7718591B2/en
Ceased legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/32Organic compounds containing nitrogen
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0073Anticorrosion compositions
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2068Ethers
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/28Heterocyclic compounds containing nitrogen in the ring
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines
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    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/32Amides; Substituted amides
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    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43Solvents
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02Inorganic compounds
    • C11D7/04Water-soluble compounds
    • C11D7/10Salts
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/261Alcohols; Phenols
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    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/32Organic compounds containing nitrogen
    • C11D7/3209Amines or imines with one to four nitrogen atoms; Quaternized amines
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    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/32Organic compounds containing nitrogen
    • C11D7/3218Alkanolamines or alkanolimines
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    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
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    • C11D7/3281Heterocyclic compounds
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    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50Solvents
    • C11D7/5004Organic solvents
    • C11D7/5009Organic solvents containing phosphorus, sulfur or silicon, e.g. dimethylsulfoxide
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50Solvents
    • C11D7/5004Organic solvents
    • C11D7/5013Organic solvents containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50Solvents
    • C11D7/5004Organic solvents
    • C11D7/5022Organic solvents containing oxygen
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/42Stripping or agents therefor
    • G03F7/422Stripping or agents therefor using liquids only
    • G03F7/423Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/42Stripping or agents therefor
    • G03F7/422Stripping or agents therefor using liquids only
    • G03F7/425Stripping 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041Cleaning
    • H01L21/02057Cleaning during device manufacture
    • H01L21/0206Cleaning during device manufacture during, before or after processing of insulating layers
    • H01L21/02063Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041Cleaning
    • H01L21/02057Cleaning during device manufacture
    • H01L21/02068Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • H01L21/02071Cleaning 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment 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
    • H01L21/3105After-treatment
    • H01L21/311Etching the insulating layers by chemical or physical means
    • H01L21/31105Etching inorganic layers
    • H01L21/31111Etching inorganic layers by chemical means
    • H01L21/31116Etching inorganic layers by chemical means by dry-etching
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment 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
    • H01L21/3105After-treatment
    • H01L21/311Etching the insulating layers by chemical or physical means
    • H01L21/31127Etching organic layers
    • H01L21/31133Etching organic layers by chemical means
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment 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
    • H01L21/3105After-treatment
    • H01L21/311Etching the insulating layers by chemical or physical means
    • H01L21/31127Etching organic layers
    • H01L21/31133Etching organic layers by chemical means
    • H01L21/31138Etching organic layers by chemical means by dry-etching
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/14Hard surfaces
    • C11D2111/22Electronic devices, e.g. PCBs or semiconductors
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    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/263Ethers
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    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/34Organic compounds containing sulfur
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S134/00Cleaning and liquid contact with solids
    • Y10S134/902Semiconductor wafer

Definitions

  • This invention relates to ammonia-free fluoride salt containing cleaning compositions for cleaning microelectronic substrates, and particularly to such cleaning compositions useful with and having improved compatibility with microelectronic substrates characterized by sensitive porous and low- ⁇ and high- ⁇ dielectrics and copper metallization.
  • the invention also relates to the use of such cleaning compositions for stripping photoresists, cleaning residues from plasma generated organic, organometallic and inorganic compounds, and cleaning residues from planarization processes, such as chemical mechanical polishing (CMP), as well as an additive in planarization slurry residues.
  • CMP chemical mechanical polishing
  • photoresist strippers and residue removers have been proposed for use in the microelectronics field as downstream or back end of the manufacturing line cleaners.
  • a thin film of photoresist is deposited on a wafer substrate, and then circuit design is imaged on the thin film.
  • the unpolymerized resist is removed with a photoresist developer.
  • the resulting image is then transferred to the underlying material, which is generally a dielectric or metal, by way of reactive plasma etch gases or chemical etchant solutions.
  • the etchant gases or chemical etchant solutions selectively attack the photoresist-unprotected area of the substrate.
  • the typical alkaline cleaning solutions employed are overly aggressive towards low- ⁇ and high- ⁇ dielectrics and/or copper metallizations.
  • many of these alkaline cleaning compositions contain organic solvents that show poor product stability, especially at higher pH ranges and at higher process temperatures.
  • compositions suitable for back end cleaning operations which compositions are effective cleaners and are applicable for stripping photoresists and cleaning plasma ash residues from plasma process generated organic, organometallic and inorganic materials.
  • This invention relates to compositions that are effective in stripping photoresists, preparing/cleaning ashed semiconductor surfaces and structures with good compatibility with advanced interconnect materials and copper metallizations.
  • ammonia NH 3
  • ammonia-derived salts such as NH 4 X where X is fluoride, fluoroborate or the like
  • NH 4 X NH 4 X
  • X fluoride, fluoroborate or the like
  • ammonium fluoride can provide nucleophilic and metal-chelating ammonia (NH 3 ) through the equilibrium process described in Equation 1 or 2, particularly when other bases such as amines and alkanolamines are added.
  • NH 3 nucleophilic and metal-chelating ammonia
  • metals such as copper can be dissolved/corroded through complex formation with ammonia, as described in Equation 3.
  • Such complex formation can further shift the equilibrium (Equation 1 or 2) to the right, and provide more ammonia, leading to higher metal dissolution/corrosion.
  • HF Hydrofluoric acid
  • Ammonia and ammonia-derived salts also show poor compatibility with sensitive dielectrics, such as hydrogen silsesquioxane (HSQ) and methyl silsesquioxane (MSQ). Again, they can provide ammonia and/or other nucleophiles, and thus lead to reaction/degradation of sensitive dielectrics.
  • Fluoride salts derived from primary or secondary amines are undesirable for sensitive low- ⁇ dielectrics. They can provide efficient nucleophiles, such as the corresponding primary and secondary amines, through mechanisms similar to the aforementioned equations 1 to 3.
  • cleaning formulations containing non- ammonium and non-HF producing producing fluoride salts show much improved compatibility with sensitive porous and low- ⁇ and high- ⁇ dielectrics and copper metallization.
  • Any suitable non-ammonium producing, non-HF producing fluoride salt can be employed in the cleaning compositions of this invention.
  • the novel back end cleaning composition of this invention will comprise one or more of any suitable non-ammonium producing, non-HF producing fluoride salt (non-ammonium, quaternary ammonium fluoride salt) in a suitable solvent.
  • suitable non-ammonia producing, non-HF producing fluoride salts there may be mentioned tetraalkylammonium fluorides of the formula (R) N + F " , where each R is independently a substituted or unsubstituted alkyl, preferably alkyl of from 1 to 22, and more preferably 1 to 6, carbon atoms (R ⁇ H), such as tetramethylammonium fluoride and tetrabutylammonium fluoride salts; as well as fluoroborates, tetrabutylammonium fluoroborates, aluminum hexafluorides, antimony fluoride and the like.
  • the non-ammonium producing, non-HF producing fluoride salts show significantly improved compatibility with low- ⁇ dielectrics and copper metallization.
  • Tetraalkylammonium salts such as tetramethylammonium fluoride (TMAF) can be blended and dissolved in water, certain anhydrous organic solvents, or water and one or more polar, water miscible organic solvents. Selection of a copper/low- ⁇ compatible "friendly" solvent is also advantageous. Any suitable solvent free of strong nucleophiles, such as unhindered primary or secondary amines, is preferably employed.
  • Preferred solvents do not include unhindered nucleophiles, and include for example, such as dimethyl sulfoxide (DMSO), sulfolane (SFL), dimethyl piperidone, 1 -(2-hydroxyethyl)-2-pyrrolidinone (HEP), 1-methyl-2-pyrrolidinone and dimethylacetamide and the like.
  • DMSO dimethyl sulfoxide
  • SFL sulfolane
  • HEP 1-methyl-2-pyrrolidinone
  • Polar nitrile-containing solvents such as acetonitrile, isobutylnitrile and the like, can be especially advantageous.
  • tetraalkylammonium fluoride salts such as for example tetramethylammrnonium fluoride (TMAF)
  • TMAF tetramethylammrnonium fluoride
  • HEP 1-(2-hydroxyethyl)-2- pyrrolidinone
  • fluoride salt-containing cleaning compositions of this invention it may in some instances be desirable to optionally include in the cleaning compositions one or more "corrosion inhibiting solvent", i.e., a solvent compound that has at least two sites capable of complexing with metal is employed.
  • a corrosion inhibiting solvent i.e., a solvent compound that has at least two sites capable of complexing with metal is employed.
  • Preferred as such corrosion inhibiting solvents are compounds having two or more sites capable of complexing with a metal and having one of the two following general formulae:
  • X is alkylene, cycloalkylene or cycloalkylene containing one or more hetero atoms selected from O, S, N and P atoms, and arylene or arylene containing one or more hetero atoms selected from O, S, N and P atoms; each R, R, and R 2 are each independently selected from hydrogen, alkyl, cycloalkyl or cycloalkyl containing one or more hetero atoms selected from O, S, N and P atoms, and aryl or aryl containing one or more hetero atoms selected from O, S, N and P atoms; each of n1 and n2 is independently an integer of from 0 to 6; and z is an integer of from 1 to 6 when X is alkylene, cycloalkylene or
  • alkyl and alkylene are preferably of from 1 to 6 carbon atoms, more preferably of from 1 to 3 carbon atoms, cycloalkyl and cycloalkylene preferably contain from 3 to 6 carbon atoms, and aryl and arylene preferably contain from about 3 to 14 carbon atoms, more preferably from about 3 to 10 carbon atoms.
  • Alkyl is preferably methyl, ethyl or propyl; alkylene is preferably methylene, ethylene or propylene; aryl is preferably phenyl; arylene is preferebly phenylene; hetero-substiituted cycloalkyl is preferably dioxyl, morpholinyl and pyrrolidinyl; and hetero-substituted aryl is preferably pyridinyl.
  • corrosion inhibiting solvents include, for example, but are not limited to ethylene glycol, diethylene glycol, glycerol, diethylene glycol dimethyl ether, monoethanolamine, diethanolamine, triethanolamine, N,N-dimethylethanolamine, 1-(2-hydroxyethyl)-2-pyrrolidinone, 4-(2- hydroxyethyl)morpholine, 2-(methylamino)ethanol, 2-amino-2-methyl-1-propanol, 1- amino-2-propanol, 2-(2-aminoethoxy)-ethanol, N-(2-hydroxyethyl) acetamide, N-(2- hydroxyethyl) succinimide and 3-(diethylamino)-1 ,2-propanediol.
  • ethylene glycol diethylene glycol, glycerol, diethylene glycol dimethyl ether, monoethanolamine, diethanolamine, triethanolamine, N,N-dimethylethanolamine, 1-(2-hydroxyethyl)-2-pyrrolidinone
  • the cleaning compositions may also contain surfactants, such as for example dimethyl hexynol (Surfynol-61),ethoxylated tetramethyl decynediol (Surfynol-465), polytetrafluoroethylene cetoxypropylbetaine (Zonyl FSK), (Zonyl FSH) and the like.
  • surfactants such as for example dimethyl hexynol (Surfynol-61),ethoxylated tetramethyl decynediol (Surfynol-465), polytetrafluoroethylene cetoxypropylbetaine (Zonyl FSK), (Zonyl FSH) and the like.
  • any suitable metal ion-free silicate may be used in the compositions of the present invention.
  • the silicates are preferably quaternary ammonium silicates, such as tetraalkyl ammonium silicate (including hydroxy- and alkoxy- containing alkyl groups generally of from 1 to 4 carbon atoms in the alkyl or alkoxy group).
  • the most preferable metal ion-free silicate component is tetramethyl ammonium silicate.
  • Other suitable metal ion-free silicate sources for this invention may be generated in-situ by dissolving any one or more of the following materials in the highly alkaline cleaner.
  • Suitable metal ion-free materials useful for generating silicates in the cleaner are solid silicon wafers, silicic acid, colloidal silica, fumed silica or any other suitable form of silicon or silica.
  • Metal silicates such as sodium metasilicate may be used but are not recommended due to the detrimental effects of metallic contamination on integrated circuits.
  • the silicates may be present in the composition in an amount of from about 0 to 10 wt. %, preferably in an amount of from about 0.1 to about 5 wt. %.
  • compositions of the present invention may also be formulated with suitable metal chelating agents to increase the capacity of the formulation to retain metals in solution and to enhance the dissolution of metallic residues on the wafer substrate.
  • the chelating agent will generally be present in the compositions in an amount of from about 0 to 5 wt. %, preferably from an amount of from about 0.1 to 2 wt. %.
  • Typical examples of chelating agents useful for this purpose are the following organic acids and their isomers and salts: (ethylenedinitrilo)tetraacetic acid (EDTA), butylenediaminetetraacetic acid, (1 ,2- cyclohexylenedinitrilo)tetraacetic acid (CyDTA), diethylenetriaminepentaacetic acid (DETPA), ethylenediaminetetrapropionic acid,
  • HEDTA hydroxyethylethylenediaminetriacetic acid
  • ETMP N,N,N',N'- ethylenediaminetetra(methylenephosphonic) acid
  • TTHA triethylenetetraminehexaacetic acid
  • DHPTA triethylenetetraminehexaacetic acid
  • NAA methyliminodiacetic acid
  • propylenediaminetetraacetic acid nitrolotriacetic acid
  • NTA citric acid, tartaric acid, gluconic acid
  • saccharic acid glyceric acid, oxalic acid, phthalic acid, maleic acid, mandelic acid, malonic acid, lactic acid, salicylic acid, catechol, gallic acid, propyl gallate, pyrogallol, 8-hydroxyquinoline, and cysteine.
  • Preferred chelating agents are aminocarboxylic acids such as EDTA, CyDTA and aminophosphoric acid (N-DTA and aminophosphoric acid)
  • the cleaning compositions of this invention containing the non- ammonium producing, non-HF producing salts can be formulated into aqueous, semi-aqueous or organic solvent-based compositions.
  • the non-ammonium producing, non-HF producing salts can be used with any suitable stable solvents, preferably one or more polar organic solvents resistant to strong bases and that do not contain unhindered nucleophiles, such as dimethyl sulfoxide (DMSO), sulfolane (SFL), dimethyl piperidone, HEP, 1-methyl-2-pyrrolidinone and dimethylacetamide and the like.
  • DMSO dimethyl sulfoxide
  • SFL sulfolane
  • dimethyl piperidone sulfolane
  • HEP 1-methyl-2-pyrrolidinone
  • dimethylacetamide and the like can be especially advantageous.
  • the cleaning composition may also optionally contain organic or inorganic acids, preferably weak organic or inorganic acids, hindered amines, hindered alkanolamines, and hindered hydroxylamines, such as triisopropylamine, and other corrosion inhibitors.
  • organic or inorganic acids preferably weak organic or inorganic acids, hindered amines, hindered alkanolamines, and hindered hydroxylamines, such as triisopropylamine, and other corrosion inhibitors.
  • a wide range of processing/operating pH and temperatures can be used to effectively remove and clean photoresist, plasma etch/ash residue, sacrifical light absorbing materials and anti-reflective coatings (ARC) from substrates with porous or low- ⁇ or high- ⁇ dielectrics or copper metallization.
  • ARC anti-reflective coatings
  • the cleaning compositions of this invention will generally comprise from about 0.05 to about 20 wt.% of the non-ammonium producing, non-HF producing fluoride salts; from about 5 to about 99.95 wt.% water or organic solvent or both water and organic solvent; from about 0 to 80 wt.& corrosion inhibiting solvent;from about 0 to 40 wt.% steric hindered amines or alkanolamines and hydroxylamines; about 0 to 40 wt.% organic or inorganic acids; and about 0 to 40 wt.% other metal corrosion inhibitor compound; about 0 to 5 wt.% of a surfactant; 0 to 10 Wt.% metal ion free silicate compound; and about 0 to 10 wt.% metal chelating agent.
  • HEP 1 -(2-hydroxyethyl)-2-pyrrolidinone
  • TMAF 20% tetramethylammonium fluoride
  • BT benzotriazole
  • DMSO dimethyl sulfoxide
  • compositions of this invention are set forth in the following Table 1.
  • interlayer dielectric (ILD) etch rates for Composition B of Table 1 against various dielectrics were evaluated by the following test procedure.
  • the film thickness of the wafer pieces is measured using a Rudolph
  • Black DiamondTM brand of carbon doped oxide
  • SiLKTM organic polymer
  • TEOS tetraethylorthosilicate
  • Fox-16TM flowable oxide (HSQ type).
  • SiN silicon nitride.
  • the copper and aluminum etch rates for cleaning compositions of this invention are demonstrated by the etch rate data in the following Tables 5 and 6.
  • the etch rate was determined utilizing the following test procedure.
  • Pieces of aluminum or copper foil of approximately 13 x 50 mm were employed. The weight of the foil pieces was measured. After cleaning the foil pieces with 2-propanol, distilled water and acetone and the foil pieces are dried in a drying oven. The cleaned, dried foil pieces were then placed in loosely capped bottles of preheated cleaning compositions of the invention and placed in a vacuum oven for a period of from two to twenty-four hours at the indicated temperature. Following treatment and removal from the oven and bottles, the cleaned foils were rinsed with copious amounts of distilled water and dried in a drying oven for about 1 hour and then permitted to cool to room temperature, and then the etch rate determined based on weight loss or weight change.
  • the copper etch rate for a composition of this invention was compared to the copper etch rate of a corresponding composition in which ammonium fluoride (NH4F) was employed in place of the tetramethylammonium fluoride component of the composition of the invention.
  • the copper etch rates of the two compositions are presented in TABLE 7.
  • the following example demonstrates the superior compatibility of the non-ammonium, quaternary ammonium fluoride salts of this invention, e.g. TMAF, in comparison to the ammonium based fluoride salts, e.g. ammonium fluoride (NH 4 F), with sensitive low- ⁇ dielectrics, such as hydrogen silsesquioxane (HSQ) type FOx-15TMflowable oxide.
  • TMAF non-ammonium, quaternary ammonium fluoride
  • NH 4 F ammonium fluoride
  • sensitive low- ⁇ dielectrics such as hydrogen silsesquioxane (HSQ) type FOx-15TMflowable oxide.
  • the test procedure is as follows. Wafer sampoles coated with dielectric films were immersed in a magnetically stirred wet chemical solution (stirring rate 300rpm), followed by isopropanol and distilled water rinses. The samples were then dried with a nitrogen stream before IR analysis
  • Transmittance IR spectra were obtained with a Nicolet 740 FTIR spectrometer using a deuterated triglycine sulfate (DTGS) detector. Spectra were acquired with 4 cm -1 resolution and averaged over 32 scans.
  • Fourier Transform Infrared (FTIR) analysis provides a way of monitoring the structural changes of HSQ dielectrics.
  • the infrared absorption band assignments of typical deposited HSQ films are as follows.
  • the content of Si-H bonds in HSQ films can be determined by measuring the peak areas of Si-H absorption bands at 2,250 cm "1 .
  • compositions of this invention compared to the cleaning capability of a commercially available cleaning composition (ATMI ST-250) is illustrated in the following tests in which a microelectronic structure that comprised a wafer of the following via structure, namely pTEOS/CoralTM carbon doped oxide/SiN/Coral/SiN/Cu, was immersed in cleaning solutions for the indicated temperature and time, were then water rinsed, dried and then the cleaning determined by SEM inspection.
  • Table 10 The results are set forth in Table 10.

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BR0210895-0A BR0210895A (pt) 2001-07-09 2002-07-08 Composições de limpeza de microeletrÈnicos contendo sais de fluoreto livres de amÈnia para remoção seletiva do fotorresiste e limpeza de resìduo de cinza de plasma
AU2002316588A AU2002316588A1 (en) 2001-07-09 2002-07-08 Microelectronic cleaning compositions containing ammonia-free fluoride salts
IL15976002A IL159760A0 (en) 2001-07-09 2002-07-08 Microelectronic cleaning compositions containing ammonia-free fluoride salts
KR1020047000267A KR101031926B1 (ko) 2001-07-09 2002-07-08 무암모니아 불화염을 포함하는 마이크로일렉트로닉 세정조성물
YU1004A RS51684B (sr) 2001-07-09 2002-07-08 Preparati za čišćenje mikroelektronike koji sadrže fluoridne soli bez amonijaka
DK02746902.2T DK1404795T3 (da) 2001-07-09 2002-07-08 Mikroelektroniske rensningssammensætninger indeholdende amoniak-fri fluoridsalte
CA2452921A CA2452921C (en) 2001-07-09 2002-07-08 Microelectronic cleaning compositions containing ammonia-free fluoride salts
US10/483,036 US7247208B2 (en) 2001-07-09 2002-07-08 Microelectronic cleaning compositions containing ammonia-free fluoride salts
EP02746902A EP1404795B1 (en) 2001-07-09 2002-07-08 Microelectronic cleaning compositions containing ammonia-free fluoride salts
DE60238258T DE60238258D1 (de) 2001-07-09 2002-07-08 Ammoniak-freie fluorid-salze enthaltende mikroelectronikreinigunsmittel
JP2003512358A JP4188232B2 (ja) 2001-07-09 2002-07-08 選択的フォトレジストストリッピングおよびプラズマ灰化残渣洗浄のための、アンモニア不含フッ化物塩含有マイクロエレクトロニクス洗浄組成物
PL368044A PL199393B1 (pl) 2001-07-09 2002-07-08 Kompozycja czyszcząca do oczyszczania podłoży stosowanych w mikroelektronice z pozostałości po trawieniu lub spopieleniu plazmowym i sposób oczyszczania podłoży stosowanych w mikroelektronice z pozostłości po trawieniu lub spopieleniu plazmowym
AT02746902T ATE487785T1 (de) 2001-07-09 2002-07-08 Ammoniak-freie fluorid-salze enthaltende mikroelectronikreinigunsmittel
IL159760A IL159760A (en) 2001-07-09 2004-01-07 Microelectronic cleaners containing ammonia-free fluoride salts
NO20040070A NO20040070L (no) 2001-07-09 2004-01-08 Mikroelektroniske rensesammensetninger inneholdende ammoniakkfrie flurodsalter
US11/762,087 US7718591B2 (en) 2001-07-09 2007-06-13 Microelectronic cleaning compositions containing ammonia-free fluoride salts for selective photoresist stripping and plasma ash residue cleaning

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