WO2009086231A2 - Post-deposition cleaning methods and formulations for substrates with cap layers - Google Patents

Post-deposition cleaning methods and formulations for substrates with cap layers Download PDF

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Publication number
WO2009086231A2
WO2009086231A2 PCT/US2008/087878 US2008087878W WO2009086231A2 WO 2009086231 A2 WO2009086231 A2 WO 2009086231A2 US 2008087878 W US2008087878 W US 2008087878W WO 2009086231 A2 WO2009086231 A2 WO 2009086231A2
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WO
WIPO (PCT)
Prior art keywords
cleaning solution
concentration
reducing agent
surface active
corrosion inhibitor
Prior art date
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Ceased
Application number
PCT/US2008/087878
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English (en)
French (fr)
Other versions
WO2009086231A3 (en
Inventor
Artur Kolics
Shijian Li
Tiruchirapalli Arunagiri
William Thie
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Lam Research Corp
Original Assignee
Lam Research Corp
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Filing date
Publication date
Application filed by Lam Research Corp filed Critical Lam Research Corp
Priority to JP2010539925A priority Critical patent/JP5804706B2/ja
Priority to CN200880127389.9A priority patent/CN101971296B/zh
Priority to KR1020167005186A priority patent/KR101698731B1/ko
Publication of WO2009086231A2 publication Critical patent/WO2009086231A2/en
Publication of WO2009086231A3 publication Critical patent/WO2009086231A3/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0085—Apparatus for treatments of printed circuits with liquids not provided for in groups H05K3/02 - H05K3/46; conveyors and holding means therefor
    • 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
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
    • H01L21/76849—Barrier, adhesion or liner layers formed in openings in a dielectric the layer being positioned on top of the main fill metal
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
    • H01L21/76861—Post-treatment or after-treatment not introducing additional chemical elements into the layer
    • 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 pertains to fabrication of electronic devices such as integrated circuits; more specifically, this invention relates to methods and formulations for cleaning substrates having cap layers containing at least one of the chemical elements cobalt and nickel on metal and dielectric damascene metallization structures.
  • a metal cap is applied to copper interconnects that are embedded in a dielectric structure to form a damascene metallization layer.
  • the surface of the metal cap and the surface of the dielectric area are preferably cleaned so as to remove contaminants and defects.
  • the metal cap should not suffer significant metal loss, or experience pitting or other forms of localized corrosion.
  • materials for the metal cap are materials such as cobalt, cobalt alloy, cobalt-nickel alloy, nickel, and nickel alloy.
  • defects such as particles and residues have to be removed from the entire wafer.
  • This invention pertains to fabrication of electronic devices.
  • One embodiment of the present invention is a method of fabricating an integrated circuit. The method includes providing a substrate having a metal and dielectric damascene metallization layer and depositing substantially on the metal a cap. After deposition of the cap, the substrate is cleaned with a solution comprising an amine to provide a pH for the cleaning solution of 7 to about 13.
  • Another embodiment of the presented invention is a method of cleaning substrates.
  • Still another embodiment of the present invention is a formulation for a cleaning solution.
  • FIG. 1 is a process flow diagram of an embodiment of the present invention.
  • the present invention pertains to interconnect metallization that uses an electrically conductive metal with a cap and a dielectric forming a damascene metallization structure for electronic devices such as integrated circuits. More preferably, the present invention pertains to interconnect metallization layers that include a dielectric and a metal, such as copper, having a cap comprising one of the chemical elements cobalt and nickel for electronic devices.
  • the operation of embodiments of the present invention will be discussed below, primarily in the context of processing semiconductor wafers such as silicon wafers used for fabricating integrated circuits.
  • the metallization layers for the integrated circuits include copper for metal lines with electrolessly deposited caps comprising at least one of the chemical elements cobalt and nickel or their alloys formed into damascene or dual damascene dielectric structures.
  • the dielectric is a low k dielectric material such as a carbon doped silicon oxide (SiOC :H).
  • SiOC carbon doped silicon oxide
  • Process flow 20 includes providing a substrate having a metal and dielectric damascene metallization, step 25.
  • Process flow 20 also includes using electroless deposition to deposit on the metal a cap comprising at least one of the chemical elements cobalt and nickel, step 35.
  • process flow 20 includes cleaning the substrate with a cleaning solution comprising an amine to provide a pH of 7 to 13 for the cleaning solution, step 40. More specifically, the amine is capable of raising the pH of the cleaning solution to a value in the range of 7 to 13 and all values and subranges subsumed therein.
  • the cleaning solution may comprise two or more amines and at least one of the two or more amines is capable of raising the pH of the cleaning solution to a value in the range of 7 to 13 and all values and subranges subsumed therein.
  • the pH of the cleaning solution is a value from about 8 to about 11.5.
  • a list of suitable compounds for amines for embodiments of the present invention includes, but is not limited to, primary alkylamines; secondary alkylamines; tertiary alkylamines; quaternary alkylamines; primary arylamines; secondary arylamines; tertiary arylamines; quaternary arylamines; ammonia; primary alkanolamines; secondary alkanolamines; tertiary alkanolamines such as ethanolamine, diethanolamine, triethanolamine, choline; amines with mixed alkyl and alkanol functionalities; tetramethylguanidine; hydroxylamine; and combinations thereof.
  • Amine molecules usually have the general formula R 3 _ X NH X where R is a hydrocarbon and 0 ⁇ x ⁇ 3.
  • Some embodiments of the present invention include one or more amines present in the cleaning solution in amounts ranging from about 1 gram per liter to about 100 grams per liter (g/L).
  • a preferred embodiment of the present invention includes deionized water in the cleaning solution.
  • cleaning the substrate includes removing contaminants, removing defects, or removing contaminants and removing defects.
  • the composition of the cleaning solution is selected so as to facilitate removal of defects and/or contaminants from the surface of the substrate, more particularly the surface of the cap and surface of the dielectric. More preferably, the composition of the cleaning solution is selected so as to clean the surface of the cap and the surface of the dielectric with negligible or substantially no reduction in the thickness of the cap.
  • the thickness of the cap is reduced by less than 15% as a result of the cleaning. More preferably, the thickness of the cap is reduced by less than 10% as a result of the cleaning. According to one embodiment of the present invention, the thickness of the cap is reduced by less than 1.5 nm.
  • Embodiments of the present invention as presented in Fig. 1 may include using a cleaning solution that contains one or more additional additives.
  • the cleaning solution further comprises one or more complexing agents and at least one of the one or more complexing agents is not an amine.
  • the complexing agent that is not an amine is referred to as a non-amine complexing agent.
  • the amine complexing agent is defined here as a chemical compound in which the only functional group in the compound that forms a complex has the general formula NRR'R" where N is a nitrogen atom and R, R', and R" can be hydrogen, alkyl or aromatic groups.
  • a list of complexing agents for embodiments of the present invention includes, but is not limited to, carboxylic acids, hydroxycarboxylic acids, amino acids, phosphonic acid, phytic acid, organic acids where Ig K for CoL > 2, and combinations thereof.
  • Some embodiments of the present invention include one or more complexing agents present in the cleaning solution in amounts ranging from about 0.5 gram per liter to about 50 grams per liter.
  • some embodiments of the present invention as presented in Fig. 1 may include using a cleaning solution that also contains one or more corrosion inhibitors to substantially protect the cap film or retard the dissolution of the cap in the cleaning solution.
  • a cleaning solution that also contains one or more corrosion inhibitors to substantially protect the cap film or retard the dissolution of the cap in the cleaning solution.
  • preferred embodiments of the present invention are capable of cleaning the substrate with negligible or substantially no reduction in the thickness of the cap; one or more corrosion inhibitor compounds may be included in embodiments of the present invention for that purpose.
  • a list of corrosion inhibitors for embodiments of the present invention includes, but is not limited to, triazole and its derivatives such as benzotriazole, methyl- benzotriazole, carboxy-benzotriazole, hydroxybenzotriazole; thiazole and its derivatives such as mercaptobenzothiazole; polyvinylpyrrolidone; polyvinylalcohol and its derivatives; polyalkylimines; polyethylenimines; long chain alkylamines; tetrazoles; orthophosphates; metaphosphates; phosphites; phosphonates; silicates; alkylphosphonates; alkoxysilanes, nitrites; bicyclohexylammonium nitrite; and combinations thereof.
  • Some embodiments of the present invention include one or more corrosion inhibitors present in the cleaning solution in amounts ranging from about 0.01 gram per liter to
  • some embodiments of the present invention as presented in Fig. 1 may include using a cleaning solution that also contains one or more oxygen scavenger compounds to remove dissolved oxygen from the cleaning solution. More specifically, the oxygen scavenger provides a lower concentration of dissolved oxygen in the cleaning solution. Preferably, the amount of dissolved oxygen is kept to a minimum so as to substantially prevent oxidation of the cap by the dissolved oxygen.
  • oxygen scavengers for dissolved oxygen in embodiments of the present invention.
  • a list of oxygen scavengers for embodiments of the present invention includes, but is not limited to, hydroxylamine and derivatives such as diethylhydroxylamine; methyl-ethylketoxime; carbohydrazide; L-ascorbic acid; D-ascorbic acid, derivatives of ascorbic acid; chlorogenic acid; hydrazine, hydrazine salts; derivatives of hydrazine; caffeic acid; phytic acid; luteolin; sulfites; and combinations thereof.
  • Some embodiments of the present invention include one or more oxygen scavengers present in the cleaning solution in amounts ranging from about 0.05 gram per liter to about 10 grams per liter. Preferred embodiments of the present invention maintain concentrations of dissolved oxygen in the cleaning solution at less than 1 part per million (ppm). For some embodiments of the present invention, the low levels of dissolved oxygen are obtained by providing a sufficient amount of one or more oxygen scavengers.
  • some embodiments of the present invention as presented in Fig. 1 may include using a cleaning solution that also contains one or more reducing agents.
  • the reducing agent is selected so as to be substantially incapable of scavenging for dissolved oxygen. More specifically, the reducing agent is selected so as to provide a function other than scavenging for dissolved oxygen in the cleaning solution.
  • a primary function of the reducing agent is to minimize unwanted anodic dissolution of the cap. This is done by the introduction of reducing agent in the cleaning solution. Depending on the type of reducing agent, the oxidation of these compounds is energetically more favorable than the oxidation and dissolution of the cap.
  • reducing agents Numerous compounds are suitable for use as reducing agents in embodiments of the present invention.
  • a list of reducing agents for embodiments of the present invention includes, but is not limited to, boron containing reducing agents, hypophosphites, thiosulf ⁇ te, aldehydes, and combinations thereof.
  • Some embodiments of the present invention include one or more reducing agents present in the cleaning solution in amounts ranging from about 0.1 gram per liter to about 10 grams per liter.
  • some embodiments of the present invention as presented in Fig. 1 may include using a cleaning solution that also contains one or more surface active agents.
  • the surface active agent is included so as to provide adequate wetting of the substrate during the cleaning.
  • the entire surface of the substrate is adequately wetted by the cleaning solution so that the dielectric areas of the substrate are wetted and the cap areas of the substrate are wetted.
  • a list of surface active agents for embodiments of the present invention includes, but is not limited to, anionic surface active agents, cationic surface active agents, nonionic surface active agents, amphoteric surface active agents, and combinations thereof.
  • Some embodiments of the present invention include one or more surface active agents present in the cleaning solution in amounts ranging from about 0.02 gram per liter to about 2 grams per liter. Preferably, if there are two or more surface active agents then each of the surface active agents is present in the cleaning solution in amounts from about 0.02 gram per liter to about 2 grams per liter.
  • some embodiments of the present invention as presented in Fig. 1 may include using a cleaning solution that also contains one or more water-soluble solvents.
  • the water-soluble solvent is included so as to perform tasks such as to help remove organic contaminants from the surface of the substrate.
  • the water-soluble solvent may also be included so as to perform tasks such as to help dissolve one or more additives included in the cleaning solution that may have a low or an insufficient solubility in water.
  • water-soluble solvents Numerous compounds are suitable for use as water-soluble solvents in embodiments of the present invention.
  • a list of water-soluble solvents for embodiments of the present invention includes, but is not limited to, primary alcohols, secondary alcohols, tertiary alcohols, polyols, ethylene glycol, dimethylsulfoxide, propylenecarbonate, and combinations thereof.
  • Some embodiments of the present invention include one or more water-soluble solvents present in the cleaning solution in amounts ranging from about 10 gram per liter to about 100 grams per liter.
  • cleaning the substrate with the cleaning solution can be performed using a brush to apply the cleaning solution to the substrate.
  • Other embodiments of the present invention can be performed that include applying the cleaning solution to the substrate without using a brush; more specifically, the cleaning solution may be applied by methods such as dipping the substrate into the cleaning solution, such as spraying the cleaning solution onto the substrate, and such as applying the solution using a proximity head.
  • the temperature for performing step 40, cleaning the substrate with a cleaning solution is preferably in the range from about 5°C to about 90 0 C.
  • the temperature of the cleaning solution is controlled.
  • the temperature of the substrate may be controlled.
  • Preferred embodiments of the present invention as presented in Fig. 1 use a cleaning solution that also includes one or more additives such as a non-amine complexing agent substantially as described supra, a corrosion inhibitor substantially as described supra, a surface active agent substantially as described supra, an oxygen scavenger substantially as described supra, a reducing agent substantially as described supra, and a water soluble solvent substantially as described supra.
  • additives such as a non-amine complexing agent substantially as described supra, a corrosion inhibitor substantially as described supra, a surface active agent substantially as described supra, an oxygen scavenger substantially as described supra, a reducing agent substantially as described supra, and a water soluble solvent substantially as described supra.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent and an amount of corrosion inhibitor.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent and an amount of oxygen scavenger.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent and an amount of reducing agent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of corrosion inhibitor, and an amount of oxygen scavenger.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of corrosion inhibitor, and an amount of reducing agent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of oxygen scavenger, and an amount of reducing agent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of oxygen scavenger, an amount of reducing agent, and an amount of corrosion inhibitor.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of corrosion inhibitor, and an amount of surface active agent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of oxygen scavenger, and an amount of surface active agent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of reducing agent, and an amount of surface active agent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of corrosion inhibitor, an amount of oxygen scavenger, and an amount of surface active agent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of corrosion inhibitor, an amount of reducing agent, and an amount of surface active agent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of oxygen scavenger, an amount of reducing agent, and an amount of surface active agent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of oxygen scavenger, an amount of reducing agent, an amount of corrosion inhibitor, and an amount of surface active agent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of corrosion inhibitor, and an amount of water-soluble solvent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of oxygen scavenger, and an amount of water-soluble solvent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of reducing agent, and an amount of water-soluble solvent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of corrosion inhibitor, an amount of oxygen scavenger, and an amount of water-soluble solvent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of corrosion inhibitor, an amount of reducing agent, and an amount of water-soluble solvent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of oxygen scavenger, an amount of reducing agent, and an amount of water-soluble solvent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of oxygen scavenger, an amount of reducing agent, an amount of corrosion inhibitor, and an amount of water-soluble solvent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of corrosion inhibitor, an amount of surface active agent, and an amount of water-soluble solvent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of oxygen scavenger, an amount of surface active agent, and an amount of water-soluble solvent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of reducing agent, an amount of surface active agent, and an amount of water-soluble solvent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of corrosion inhibitor, an amount of oxygen scavenger, an amount of surface active agent, and an amount of water-soluble solvent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of corrosion inhibitor, an amount of reducing agent, an amount of surface active agent, and an amount of water-soluble solvent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of oxygen scavenger, an amount of reducing agent, an amount of surface active agent, and an amount of water-soluble solvent.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an amount of oxygen scavenger, an amount of reducing agent, an amount of corrosion inhibitor, an amount of surface active agent, and an amount of water-soluble solvent.
  • the cleaning solution presented in Fig. 1 including a corrosion inhibitor present in a concentration between about 0.01 g/L to about 10 g/L and an oxygen scavenger present in a concentration between about 0.05 g/L to about 10 g/L.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, a corrosion inhibitor present at a concentration between about 0.01 g/L to about 20 g/L and a reducing agent present at a concentration between about 0.1 g/L to about 10 g/L.
  • the cleaning solution presented in Fig. 1 including an amount of complexing agent, an oxygen scavenger present at a concentration between about 0.05 g/L to about 10 g/L, and a reducing agent present at a concentration between about 0.1 g/L to about 10 g/L.
  • the cleaning solution presented in Fig. 1 including an amount of a complexing agent, a corrosion inhibitor present at a concentration between about 0.01 g/L to about 20 g/L, an oxygen scavenger present at a concentration between about 0.05 g/L to about 10 g/L, and a reducing agent present at a concentration between about 0.1 g/L to about 10 g/L.
  • the cleaning solution presented in Fig. 1 including an amount of non-amine complexing agent, an amount of corrosion inhibitor, an amount of surface active agent, an amount of oxygen scavenger, an amount of reducing agent, and an amount of water soluble solvent.
  • the cleaning solution presented in Fig. 1 having the amine at a concentration from about 1 g/L to about 100 g/L and the cleaning solution also including at least one of: an amount of non-amine complexing agent, an amount of corrosion inhibitor, an amount of surface active agent, an amount of oxygen scavenger, an amount of reducing agent, and an amount of water soluble solvent.
  • the cleaning solution presented in Fig. 1 having the amine at a concentration from about 1 g/L to about 100 g/L and the cleaning solution also including an amount of non-amine complexing agent, an amount of corrosion inhibitor, an amount of surface active agent, an amount of oxygen scavenger, an amount of reducing agent, and an amount of water soluble solvent.
  • the cleaning solution presented in Fig. 1 having the amine at a concentration from about 1 g/L to about 100 g/L and the cleaning solution also including at least one of: a non-amine complexing agent at a concentration from about 0.5 g/L to about 50 g/L; a corrosion inhibitor at a concentration from about 0.01 g/L to about 20 g/L; a surface active agent at a concentration of 0.02 to 2 g/L; an oxygen scavenger at a concentration from about 0.05 g/L to about 10 g/L; a reducing agent at a concentration from about 0.1 g/L to about 10 g/L; and a water soluble solvent at a concentration from about 10 g/L to about 100 g/L.
  • a non-amine complexing agent at a concentration from about 0.5 g/L to about 50 g/L
  • a corrosion inhibitor at a concentration from about 0.01 g/L to about 20 g/L
  • a surface active agent at
  • the cleaning solution presented in Fig. 1 having the amine at a concentration from about 1 g/L to about 100 g/L and the cleaning solution also including a non-amine complexing agent at a concentration from about 0.5 g/L to about 50 g/L; a corrosion inhibitor at a concentration from about 0.01 g/L to about 20 g/L; a surface active agent at a concentration of 0.02 g/L to 2 g/L; an oxygen scavenger at a concentration from about 0.05 g/L to about 10 g/L; a reducing agent at a concentration from about 0.1 g/L to about 10 g/L; and a water soluble solvent at concentration from about 10 g/L to about 100 g/L.
  • a non-amine complexing agent at a concentration from about 0.5 g/L to about 50 g/L
  • a corrosion inhibitor at a concentration from about 0.01 g/L to about 20 g/L
  • a surface active agent at a concentration of
  • any of the cleaning solution compositions can be applied to the substrate using a brush.
  • any of the cleaning solution compositions can be applied to the substrate by methods other than using a brush.
  • any of the cleaning solution compositions, such as the cleaning solution compositions presented supra can be used at temperatures in the range from about 5 0 C to about 90 0 C to clean the substrate.
  • step 40 cleaning the substrate, is performed using cleaning solution compositions described supra and the concentration of dissolved oxygen in the cleaning solution is maintained at less than about 1 part per million. This means that for any of the selected cleaning solutions for embodiments of the present invention, it is preferred that the dissolved oxygen concentration in the cleaning solution is maintained at less than about 1 part per million when cleaning the substrate.
  • Another embodiment of the present invention comprises a method of cleaning a substrate for electronic devices. More specifically, it is a method of cleaning a substrate having copper and dielectric damascene metallization.
  • the surface of the copper has a cap that includes cobalt, cobalt alloy, nickel, nickel alloy, or cobalt-nickel alloy.
  • the method comprises applying a cleaning solution to the substrate to remove defects and/or contamination with negligible dissolution of the cap, the solution comprises one or more amines, at least one of the one or more amines provides a pH from 7 to 13 in the cleaning solution.
  • the pH of the cleaning solution is a value from about 8 to about 11.5.
  • cleaning the substrate includes removing contaminants, removing defects, or removing contaminants and removing defects.
  • the composition of the cleaning solution is selected so as to facilitate removal of defects and/or contaminants from the surface of the substrate, more particularly the surface of the cap and surface of the dielectric. More preferably, the composition of the cleaning solution is selected so as to clean the surface of the cap and the surface of the dielectric with negligible or substantially no reduction in the thickness of the cap.
  • thickness of the cap is reduced by less than 15% as a result of the cleaning. More preferably, the thickness of the cap is reduced by less than 10% as a result of the cleaning. According to one embodiment of the present invention, the thickness of the cap is reduced by less than 1.5 nm.
  • Preferred embodiments of the method of cleaning substrates use a cleaning solution that also includes one or more additives such as a complexing agent substantially as described supra, a corrosion inhibitor substantially as described supra, a surface active agent substantially as described supra, an oxygen scavenger substantially as described supra, a reducing agent substantially as described supra, and a water soluble solvent substantially as described supra.
  • additives such as a complexing agent substantially as described supra, a corrosion inhibitor substantially as described supra, a surface active agent substantially as described supra, an oxygen scavenger substantially as described supra, a reducing agent substantially as described supra, and a water soluble solvent substantially as described supra.
  • the cleaning solution comprises an amine at a concentration from about 1 g/L to about 100 g/L to provide a pH for the cleaning solution of 7 to 13 and all values and subranges subsumed therein. More specifically, the amine is capable of raising the pH of the solution to a value above 7 and less than about 13. According to a preferred embodiment of the present invention, the pH of the cleaning solution is a value from about 8 to about 11.5.
  • the solution also includes at least one additive selected from the group consisting of: a non-amine complexing agent at a concentration from about 0.5 g/L to about 50 g/L; a corrosion inhibitor at a concentration from about 0.01 g/L to about 20 g/L; a surface active agent at a concentration of 0.02 g/L to 2 g/L; an oxygen scavenger at a concentration from about 0.05 g/L to about 10 g/L; a reducing agent at a concentration from about 0.1 g/L to about 10 g/L, the reducing agent having substantially no oxygen scavenging properties ; and a water soluble solvent at a concentration from about 10 to about 100 g/L.
  • a non-amine complexing agent at a concentration from about 0.5 g/L to about 50 g/L
  • a corrosion inhibitor at a concentration from about 0.01 g/L to about 20 g/L
  • a surface active agent at a concentration of 0.02 g/L to
  • the cleaning solution also includes at least two additives selected from the group consisting of a non-amine complexing agent at a concentration from about 0.5 g/L to about 50 g/L; a corrosion inhibitor at a concentration from about 0.01 g/L to about 20 g/L; a surface active agent at a concentration of 0.02 g/L to 2 g/L; an oxygen scavenger at a concentration from about 0.05 g/L to about 10 g/L; a reducing agent at a concentration from about 0.1 g/L to about 10 g/L, the reducing agent having substantially no oxygen scavenging properties ; and a water soluble solvent at a concentration from about 10 g/L to about 100 g/L.
  • a non-amine complexing agent at a concentration from about 0.5 g/L to about 50 g/L
  • a corrosion inhibitor at a concentration from about 0.01 g/L to about 20 g/L
  • a surface active agent at a concentration of 0.02
  • the cleaning solution also includes at least three additives selected from the group consisting of a non-amine complexing agent at a concentration from about 0.5 g/L to about 50 g/L; a corrosion inhibitor at a concentration from about 0.01 g/L to about 20 g/L; a surface active agent at a concentration of 0.02 g/L to 2 g/L; an oxygen scavenger at a concentration from about 0.05 g/L to about 10 g/L; a reducing agent at a concentration from about 0.1 g/L to about 10 g/L, the reducing agent having substantially no oxygen scavenging properties ; and a water soluble solvent at a concentration from about 10 g/L to about 100 g/L.
  • a non-amine complexing agent at a concentration from about 0.5 g/L to about 50 g/L
  • a corrosion inhibitor at a concentration from about 0.01 g/L to about 20 g/L
  • a surface active agent at a concentration of 0.02
  • the cleaning solution also includes at least four additives selected from the group consisting of a non-amine complexing agent at a concentration from about 0.5 g/L to about 50 g/L; a corrosion inhibitor at a concentration from about 0.01 g/L to about 20 g/L; a surface active agent at a concentration of 0.02 g/L to 2 g/L; an oxygen scavenger at a concentration from about 0.05 g/L to about 10 g/L; a reducing agent at a concentration from about 0.1 g/L to about 10 g/L, the reducing agent having substantially no oxygen scavenging properties; and a water soluble solvent at a concentration from about 10 g/L to about 100 g/L.
  • a non-amine complexing agent at a concentration from about 0.5 g/L to about 50 g/L
  • a corrosion inhibitor at a concentration from about 0.01 g/L to about 20 g/L
  • a surface active agent at a concentration of 0.02
  • Another embodiment of the present invention is a cleaning solution for an integrated circuit substrate.
  • the cleaning solution comprises an amine to provide a pH for the cleaning solution of 7 to 13 and all values and subranges subsumed therein, a complexing agent, a corrosion inhibitor, a surface active agent, an oxygen scavenger, a reducing agent, and a water soluble solvent.
  • a complexing agent e.g., a corrosion inhibitor, a corrosion inhibitor, e.g., a corrosion inhibitor, a surface active agent, an oxygen scavenger, a reducing agent, and a water soluble solvent.
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “at least one of,” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a process, method, article, or apparatus that comprises a list of elements is not necessarily limited only to those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
  • "or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

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  • Wood Science & Technology (AREA)
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KR1020167005186A KR101698731B1 (ko) 2007-12-21 2008-12-20 캡 층을 갖는 기판에 대한 증착후 세정 방법 및 제제

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2199379A1 (en) * 2008-12-17 2010-06-23 Air Products And Chemicals, Inc. Wet clean compositions for CoWP and porous dielectrics
US8404626B2 (en) 2007-12-21 2013-03-26 Lam Research Corporation Post-deposition cleaning methods and formulations for substrates with cap layers
JP2013515855A (ja) * 2009-12-23 2013-05-09 ラム リサーチ コーポレーション 堆積後ウエハ洗浄配合物
US9691622B2 (en) 2008-09-07 2017-06-27 Lam Research Corporation Pre-fill wafer cleaning formulation

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9058975B2 (en) * 2006-06-09 2015-06-16 Lam Research Corporation Cleaning solution formulations for substrates
US7772128B2 (en) * 2006-06-09 2010-08-10 Lam Research Corporation Semiconductor system with surface modification
US8444768B2 (en) * 2009-03-27 2013-05-21 Eastman Chemical Company Compositions and methods for removing organic substances
US8614053B2 (en) 2009-03-27 2013-12-24 Eastman Chemical Company Processess and compositions for removing substances from substrates
US8309502B2 (en) * 2009-03-27 2012-11-13 Eastman Chemical Company Compositions and methods for removing organic substances
KR20100110123A (ko) * 2009-04-02 2010-10-12 삼성전자주식회사 반도체 소자의 제조 방법
US8632628B2 (en) 2010-10-29 2014-01-21 Lam Research Corporation Solutions and methods for metal deposition
US9029268B2 (en) 2012-11-21 2015-05-12 Dynaloy, Llc Process for etching metals
US8603913B1 (en) * 2012-12-20 2013-12-10 Lam Research Corporation Porous dielectrics K value restoration by thermal treatment and or solvent treatment
JP6751015B2 (ja) * 2013-03-15 2020-09-02 キャボット マイクロエレクトロニクス コーポレイション 銅の化学的機械的平坦化後のための水性清浄化組成物
CN105849245B (zh) 2013-10-21 2020-03-13 富士胶片电子材料美国有限公司 用于去除表面上残余物的清洗调配物
EP3104398B1 (en) 2013-12-06 2020-03-11 Fujifilm Electronic Materials USA, Inc. Cleaning formulation and method for removing residues on surfaces
KR20170036708A (ko) * 2014-07-18 2017-04-03 캐보트 마이크로일렉트로닉스 코포레이션 디알킬히드록실아민을 사용한 트리스(2-히드록시에틸)메틸암모늄 히드록시드의 분해 안정화
CN106661518B (zh) * 2014-07-18 2020-01-14 嘉柏微电子材料股份公司 在cmp后使用的清洁组合物及其相关方法
JP6486652B2 (ja) * 2014-10-31 2019-03-20 東京応化工業株式会社 リソグラフィー用洗浄液、及び基板の洗浄方法
US10301580B2 (en) * 2014-12-30 2019-05-28 Versum Materials Us, Llc Stripping compositions having high WN/W etching selectivity
KR101854510B1 (ko) 2015-12-11 2018-05-03 삼성에스디아이 주식회사 금속 배선 연마용 cmp 슬러리 조성물 및 이를 이용한 연마 방법
CN110249041A (zh) * 2017-02-10 2019-09-17 富士胶片电子材料美国有限公司 清洗制剂
GB2567456B (en) 2017-10-12 2021-08-11 Si Group Switzerland Chaa Gmbh Antidegradant blend
CN108377615B (zh) * 2018-03-15 2020-12-29 昆山长优电子材料有限公司 用于pcb图形转移前处理制程的铜面键合溶液
EP3774680B1 (en) 2018-03-28 2025-09-24 FUJIFILM Electronic Materials U.S.A, Inc. Cleaning compositions
GB201807302D0 (en) 2018-05-03 2018-06-20 Addivant Switzerland Gmbh Antidegradant blend
JP6858209B2 (ja) * 2019-02-20 2021-04-14 東京応化工業株式会社 リソグラフィー用洗浄液、及び基板の洗浄方法
CN110003996B (zh) * 2019-05-21 2021-03-23 广东剑鑫科技股份有限公司 一种浸泡液及其制备方法和使用方法
WO2021044774A1 (ja) 2019-09-02 2021-03-11 富士フイルム株式会社 処理液、被処理物の処理方法
US12139693B2 (en) 2020-01-28 2024-11-12 Fujifilm Corporation Treatment liquid and method for treating object to be treated

Family Cites Families (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5909742A (en) 1993-03-26 1999-06-08 Betzdearborn Inc. Metal cleaning method
TW416987B (en) 1996-06-05 2001-01-01 Wako Pure Chem Ind Ltd A composition for cleaning the semiconductor substrate surface
US20010052351A1 (en) 1998-09-29 2001-12-20 Brian J. Brown Method for cleaning semiconductor wafer having copper structure formed thereon
JP2002069495A (ja) * 2000-06-16 2002-03-08 Kao Corp 洗浄剤組成物
US6599370B2 (en) * 2000-10-16 2003-07-29 Mallinckrodt Inc. Stabilized alkaline compositions for cleaning microelectronic substrates
JP4942263B2 (ja) 2001-08-31 2012-05-30 ラムリサーチ株式会社 洗浄装置
US6913651B2 (en) 2002-03-22 2005-07-05 Blue29, Llc Apparatus and method for electroless deposition of materials on semiconductor substrates
US6875691B2 (en) 2002-06-21 2005-04-05 Mattson Technology, Inc. Temperature control sequence of electroless plating baths
JP4261931B2 (ja) * 2002-07-05 2009-05-13 株式会社荏原製作所 無電解めっき装置および無電解めっき後の洗浄方法
US6846519B2 (en) 2002-08-08 2005-01-25 Blue29, Llc Method and apparatus for electroless deposition with temperature-controlled chuck
KR100536593B1 (ko) 2002-12-05 2005-12-14 삼성전자주식회사 선택적인 막 제거를 위한 세정 용액 및 그 세정 용액을사용하여 실리사이드 공정에서 막을 선택적으로 제거하는방법
TWI258504B (en) * 2003-01-07 2006-07-21 Tosoh Corp Washing solution and washing method using the same
JP4419528B2 (ja) * 2003-01-07 2010-02-24 東ソー株式会社 洗浄液及びそれを用いた洗浄方法
US6911067B2 (en) 2003-01-10 2005-06-28 Blue29, Llc Solution composition and method for electroless deposition of coatings free of alkali metals
US6902605B2 (en) 2003-03-06 2005-06-07 Blue29, Llc Activation-free electroless solution for deposition of cobalt and method for deposition of cobalt capping/passivation layer on copper
US6794288B1 (en) 2003-05-05 2004-09-21 Blue29 Corporation Method for electroless deposition of phosphorus-containing metal films onto copper with palladium-free activation
KR100672933B1 (ko) 2003-06-04 2007-01-23 삼성전자주식회사 세정 용액 및 이를 이용한 반도체 소자의 세정 방법
US7883739B2 (en) 2003-06-16 2011-02-08 Lam Research Corporation Method for strengthening adhesion between dielectric layers formed adjacent to metal layers
WO2005038084A2 (en) * 2003-10-17 2005-04-28 Applied Materials, Inc. Selective self-initiating electroless capping of copper with cobalt-containing alloys
TWI362415B (en) 2003-10-27 2012-04-21 Wako Pure Chem Ind Ltd Novel detergent and method for cleaning
US7205233B2 (en) * 2003-11-07 2007-04-17 Applied Materials, Inc. Method for forming CoWRe alloys by electroless deposition
US20050181226A1 (en) * 2004-01-26 2005-08-18 Applied Materials, Inc. Method and apparatus for selectively changing thin film composition during electroless deposition in a single chamber
US7435712B2 (en) * 2004-02-12 2008-10-14 Air Liquide America, L.P. Alkaline chemistry for post-CMP cleaning
US20050205835A1 (en) 2004-03-19 2005-09-22 Tamboli Dnyanesh C Alkaline post-chemical mechanical planarization cleaning compositions
JP4390616B2 (ja) 2004-04-27 2009-12-24 Ｎｅｃエレクトロニクス株式会社 洗浄液及び半導体装置の製造方法
US20070054482A1 (en) * 2004-08-10 2007-03-08 Takahito Nakajima Semiconductor device fabrication method
JP2007165514A (ja) * 2005-12-13 2007-06-28 Toshiba Corp 半導体装置の製造方法
JP2006106616A (ja) * 2004-10-08 2006-04-20 Tokyo Ohka Kogyo Co Ltd ホトレジスト除去用処理液および基板の処理方法
JP2006178423A (ja) * 2004-11-25 2006-07-06 Kyowa Hakko Chemical Co Ltd 化学増幅ポジ型レジスト組成物
US7247579B2 (en) 2004-12-23 2007-07-24 Lam Research Corporation Cleaning methods for silicon electrode assembly surface contamination removal
US7273813B2 (en) 2005-02-08 2007-09-25 Applied Materials, Inc. Wafer cleaning solution for cobalt electroless application
KR20080025697A (ko) * 2005-05-26 2008-03-21 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 구리를 부동태화하는 ｃｍｐ후 세정 조성물 및 이용 방법
WO2007088848A1 (ja) * 2006-02-01 2007-08-09 Tohoku University 半導体装置の製造方法及び半導体表面のマイクロラフネス低減方法
JP2007250915A (ja) * 2006-03-16 2007-09-27 Ebara Corp 基板処理方法および基板処理装置
US8685909B2 (en) 2006-09-21 2014-04-01 Advanced Technology Materials, Inc. Antioxidants for post-CMP cleaning formulations
US20080076688A1 (en) * 2006-09-21 2008-03-27 Barnes Jeffrey A Copper passivating post-chemical mechanical polishing cleaning composition and method of use
TWI454574B (zh) * 2007-05-17 2014-10-01 Advanced Tech Materials 用於化學機械研磨後（ｐｏｓｔ－ＣＭＰ）清洗配方之新穎抗氧化劑
US8404626B2 (en) 2007-12-21 2013-03-26 Lam Research Corporation Post-deposition cleaning methods and formulations for substrates with cap layers

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8404626B2 (en) 2007-12-21 2013-03-26 Lam Research Corporation Post-deposition cleaning methods and formulations for substrates with cap layers
US8790465B2 (en) 2007-12-21 2014-07-29 Lam Research Corporation Post-deposition cleaning methods for substrates with cap layers
US9691622B2 (en) 2008-09-07 2017-06-27 Lam Research Corporation Pre-fill wafer cleaning formulation
EP2199379A1 (en) * 2008-12-17 2010-06-23 Air Products And Chemicals, Inc. Wet clean compositions for CoWP and porous dielectrics
US8361237B2 (en) 2008-12-17 2013-01-29 Air Products And Chemicals, Inc. Wet clean compositions for CoWP and porous dielectrics
JP2013515855A (ja) * 2009-12-23 2013-05-09 ラム リサーチ コーポレーション 堆積後ウエハ洗浄配合物
US9476018B2 (en) 2009-12-23 2016-10-25 Lam Research Corporation Wafer cleaning formulation

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US20090162537A1 (en) 2009-06-25
KR20100108397A (ko) 2010-10-06
JP2014088569A (ja) 2014-05-15
CN101971296B (zh) 2012-05-30
US8404626B2 (en) 2013-03-26
KR101698731B1 (ko) 2017-01-20
US20130323410A1 (en) 2013-12-05
KR101633940B1 (ko) 2016-06-27
JP5804706B2 (ja) 2015-11-04
CN101971296A (zh) 2011-02-09
TWI528426B (zh) 2016-04-01
US8790465B2 (en) 2014-07-29
JP2011508438A (ja) 2011-03-10
TW200945424A (en) 2009-11-01
KR20160030326A (ko) 2016-03-16
WO2009086231A3 (en) 2009-08-27

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