WO2023282287A1 - Composition d'agent de nettoyage pour une étape post-cmp - Google Patents

Composition d'agent de nettoyage pour une étape post-cmp Download PDF

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WO2023282287A1
WO2023282287A1 PCT/JP2022/026835 JP2022026835W WO2023282287A1 WO 2023282287 A1 WO2023282287 A1 WO 2023282287A1 JP 2022026835 W JP2022026835 W JP 2022026835W WO 2023282287 A1 WO2023282287 A1 WO 2023282287A1
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Prior art keywords
post
cleaning composition
group
cmp
acid
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PCT/JP2022/026835
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English (en)
Japanese (ja)
Inventor
大輔 殿谷
千帆 水島
尊子 張替
裕大 藤井
スリャデバラ ヴィ． バブ
ジフーン ソ
スリ シヴァ ラマ クリシュナ ハヌップ ヴェギ
アリ オスマン
ゴラハリー アルンクマール ベンカタロナパ
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株式会社日本触媒
クラークソン ユニバーシティ
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Priority claimed from JP2021113728A external-priority patent/JP2023009994A/ja
Priority claimed from JP2021113727A external-priority patent/JP2023009993A/ja
Application filed by 株式会社日本触媒, クラークソン ユニバーシティ filed Critical 株式会社日本触媒
Publication of WO2023282287A1 publication Critical patent/WO2023282287A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting

Definitions

  • the present invention relates to a cleaning composition after the CMP step in semiconductor manufacturing processes. More specifically, the present invention relates to a post-CMP cleaning composition that is excellent in removing metal residues and organic residues and suppressing their adhesion, as well as in corrosion suppression.
  • CMP Chemical-Mechanical-Planarization/Polishing
  • CMP is a type of wafer surface planarization technology in the semiconductor manufacturing process, using chemical abrasives and polishing pads, chemical action and mechanical polishing It is a polishing technology that grinds the unevenness of the wafer surface and flattens it by the combined action of Metal residues such as abrasive grains and polishing dust remain on the flattened wafer surface after polishing.
  • a protective film is formed with an anticorrosive agent, and the components of the protective film may remain as organic residues after polishing. Since these residues adversely affect the electrical properties of semiconductors, etc., post-CMP cleaning is performed to remove the residues.
  • Post-CMP cleaning is usually performed by combining chemical cleaning using a cleaning agent and physical cleaning using a brush or the like.
  • a cleaning agent a cleaning composition containing a main component, a chelating agent, a surfactant and the like is usually used.
  • Patent Document 1 discloses a working liquid useful for modifying a wafer surface, which contains water, a pH buffering agent containing a basic pH adjuster and an acidic complexing agent, and a surfactant, and has a pH of 7 to 12.
  • Patent Document 2 describes a cleaning agent for substrates having metal wiring, which contains an aqueous solution having a pH of 10 or more and containing a carboxylic acid having a nitrogen-containing heterocycle and an alkylhydroxylamine.
  • Patent Document 3 one or more kinds of basic compounds and one or more kinds of heterocyclic monocyclic aromatic compounds containing a nitrogen atom are included, and the hydrogen ion concentration (pH) is 8 to 11, and Patent Document 4 describes a semiconductor containing a compound having an amine group and a carboxyl group, adenine, purine, uric acid, derivatives thereof, etc., a pH adjuster, and water. A substrate cleaning solution for devices is described.
  • Patent Document 5 a specific organic quaternary ammonium hydroxide, a surfactant, a chelating agent, an amino acid having a sulfur atom and/or a derivative thereof, benzotriazole, imidazole, triazole, A semiconductor device substrate cleaning liquid containing at least one selected from the group consisting of tetrazole and derivatives thereof and having a pH of 9 or more is disclosed.
  • Patent Document 6 describes a cleaning liquid that can reduce cerium compounds remaining on a substrate more safely and easily than the conventional technique, comprising water, sugars exhibiting reducing properties in an alkaline atmosphere, and an alkaline component. and has a pH of 7 or higher at 25°C.
  • Patent Document 7 describes at least one selected from the group consisting of alkanolamine compounds and heterocyclic amine compounds, and a quaternary ammonium
  • a cleaning solution for cleaning semiconductor wafers is described that includes hydroxide, citric acid, and ascorbic acid.
  • a polishing slurry containing ceria (cerium oxide: CeO 2 ) particles is used to perform CMP on a SiO 2 substrate, Si—O—Ce bonds are formed on the substrate, leaving ceria particles on the substrate.
  • ceria cerium oxide: CeO 2
  • a component such as hydrogen peroxide that requires careful handling.
  • a semiconductor wafer has deposited layers such as a metal film and an insulating film that become wiring on a substrate, and various metal compound materials including copper, cobalt, tantalum, tungsten, titanium, etc. are used for these.
  • the post-CMP cleaning composition can exhibit excellent cleaning function and corrosion inhibiting function for these metal compound materials as well. is desirable. Furthermore, in recent years, semiconductor devices have become increasingly faster and more highly integrated, and there is a demand for even more advanced CMP processing characteristics. Thus, there has been a need for a post-cleaning composition for CMP processes that can simultaneously solve these problems as well as the CMP processing properties.
  • the present invention has been made in view of the above-mentioned current situation, and is a post-CMP cleaning composition that is excellent in removing and inhibiting adhesion of metal residues and organic residues remaining on a polished surface of a flattened substrate, and is also excellent in inhibiting corrosion.
  • the purpose is to provide goods.
  • the present inventors have conducted various studies on post-cleaning compositions for the CMP process, and found that a specific nonionic surfactant and/or N-vinyllactam polymer and an aliphatic amine , and a specific corrosion inhibitor, the removal of metal residues and organic residues and the adhesion-inhibiting action are remarkably improved, and the corrosion-inhibiting action is also excellent. Further, by using a combination of a specific nonionic surfactant and/or N-vinyllactam polymer, an organic acid compound, and a pH adjuster, it is possible to perform the CMP process using ceria as polishing abrasive grains. It was found that the removal and adhesion suppression of metal residues and organic residues on the surface of the wafer that was carried out were remarkably improved, and the corrosion suppression was also excellent. Based on these findings, the inventors have made intensive studies and completed the present invention.
  • the first present invention provides (1A) at least one selected from the group consisting of a nonionic surfactant containing an alkylene oxide adduct of an alcohol having 6 or more carbon atoms, and an N-vinyl lactam polymer. , (1B) aliphatic amines, and (1C) at least one corrosion inhibitor selected from the group consisting of nitrogen-containing heterocyclic compounds and carboxylate compounds. is a post-cleaning composition for the CMP process in.
  • the above aliphatic amines preferably have a molecular weight of 2000 or less.
  • the aliphatic amines preferably contain an amine compound represented by the following general formula (1) and/or a polyalkyleneimine.
  • R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, an alkyl group, or —R 4 —(NH—R 5 ) n —NH 2.
  • R 4 and R 5 is the same or different and represents an alkylene group having 1 to 6 carbon atoms, and n represents an integer of 0 to 100.
  • the nitrogen-containing heterocyclic compound preferably contains at least one selected from the group consisting of pyrrole, pyridine, triazole, triazine, purine, and derivatives thereof.
  • the carboxylate compound preferably contains a fatty acid salt.
  • the post-CMP cleaning composition is suitable for use on wafer surfaces where a compound containing at least one selected from the group consisting of cobalt, copper, aluminum, ruthenium, titanium nitride, silicon nitride, and silicon oxide is exposed. It is preferably used for washing.
  • the second aspect of the present invention provides (2A) at least one compound selected from the group consisting of a nonionic surfactant having an alkylene oxide adduct structure of an aliphatic alcohol, and an N-vinyllactam polymer. , (2B) an organic acid compound, and (2C) a pH adjuster.
  • the content of the oxidizing agent in the post-CMP cleaning composition is preferably 1.0% by mass or less with respect to 100% by mass of the post-CMP cleaning composition.
  • the aliphatic alcohol alkylene oxide adduct structure preferably has an alkylene oxide adduct structure of an aliphatic alcohol having 6 or more carbon atoms, and includes block polymer structures of two or more alkylene oxides.
  • the aliphatic alcohol is preferably a secondary or tertiary alkyl alcohol having 6 or more carbon atoms.
  • the pH adjuster is preferably a basic pH adjuster.
  • the basic pH adjuster preferably contains at least one compound selected from the group consisting of hydroxides, organic amines, organic amine salts, and ammonium salts.
  • the organic acid compound preferably contains at least one compound selected from the group consisting of carboxylic acid compounds and ascorbic acid.
  • the post-CMP cleaning composition is preferably a post-CMP cleaning composition using ceria as abrasive grains.
  • the post-CMP cleaning composition is preferably used for cleaning the surface of a film containing silicon oxide and/or silicon nitride in a semiconductor manufacturing process.
  • the post-cleaning composition for the CMP process of the present invention is excellent in removing and preventing adhesion of metal residues and organic residues on the wafer surface, and is also excellent in suppressing corrosion.
  • the post-CMP cleaning composition of the present invention can be suitably used as a post-CMP cleaning composition in semiconductor manufacturing processes.
  • FIG. 1 is an AFM observation image of the surface of a substrate for cleaning evaluation when cleaning performance evaluation of the cleaning compositions of Examples 1 to 3 and Comparative Examples 1 and 2 is performed.
  • cleaning compositions of Examples 11 to 12, 17 to 18, and Comparative Examples 4 and 5 cleaning treatment of SiO 2 substrates A-1 and A-2 for cleaning performance evaluation and non-cleaning.
  • 4 is an AFM image showing the surface condition of the substrate.
  • FIG. 10 is an AFM image showing the surface state of the SiO 2 substrates A-1 and A-2 for evaluating cleaning performance when the cleaning compositions of Examples 13 to 15 and Comparative Example 6 were used to clean the substrates.
  • FIG. An AFM showing the surface state of the SiN substrates B-1 and B-2 for cleaning performance evaluation with and without cleaning using the cleaning compositions of Examples 11, 13 and 16. It is an image.
  • a first aspect of the present invention provides (1A) at least one compound selected from the group consisting of a nonionic surfactant containing an alkylene oxide adduct of an alcohol having 6 or more carbon atoms, and an N-vinyllactam polymer. , (1B) aliphatic amines, and (1C) at least one corrosion inhibitor selected from the group consisting of nitrogen-containing heterocyclic compounds and carboxylate compounds in a semiconductor manufacturing process, A post-cleaning composition for a CMP process.
  • the second aspect of the present invention provides (2A) at least one compound selected from the group consisting of a nonionic surfactant having an alkylene oxide adduct structure of an aliphatic alcohol, and an N-vinyllactam polymer. , (2B) an organic acid compound, and (2C) a pH adjuster.
  • a nonionic surfactant having an alkylene oxide adduct structure of an aliphatic alcohol, and an N-vinyllactam polymer.
  • (2B) an organic acid compound an organic acid compound
  • (2C) a pH adjuster a pH adjuster.
  • the first post-CMP cleaning composition of the present invention contains the above-described three specific components (1A), (1B) and (1C) to remove and suppress adhesion of metal residues and organic residues. It is also excellent in corrosion control.
  • the first post-cleaning composition for the CMP process of the present invention is excellent in removing and inhibiting the adhesion of metal residues and organic residues, and is also excellent in inhibiting corrosion.
  • the nonionic surfactant or N-vinyllactam polymer contained in the surfactant permeates the surface of the substrate and the interface of the abrasive residue and dirt, causing it to float in the water, which is the main component of the cleaning liquid, while the aliphatic amines are highly distributed to the heavy metal ions. This is presumed to be due to the ability to reduce the adsorptive power of the polishing residue to the fresh metal surface exposed in the CMP process.
  • the adsorption of the nitrogen-containing heterocyclic compound and the carboxylate compound on the surface of the deposited metal film allows the electrochemical interaction between the chemical components coexisting in the cleaning composition to be in an equilibrium state, thereby forming the deposited metal film. It is presumed that the corrosion potential and corrosion current value of the metal species constituting the can be reduced.
  • the components contained in the first post-CMP cleaning composition will be described.
  • the first post-cleaning composition for the CMP step is a nonionic surfactant containing an alkylene oxide adduct of an alcohol having 6 or more carbon atoms. , and at least one compound selected from the group consisting of N-vinyllactam polymers (hereinafter also referred to as “compound (1A)” or “component (1A)”).
  • compound (1A) N-vinyllactam polymers
  • Ionic surfactants such as cationic or anionic surfactants are ionic, and are remarkably adsorbed due to electrostatic interaction with the cleaned substrate. It may become a contaminant when commercialized.
  • nonionic surfactants and N-vinyllactam polymers have little electrostatic interaction due to their lack of ionicity, and are rinsed with pure water even when they are adsorbed on the cleaned substrate surface after the CMP process. can be easily removed by Therefore, in the present invention, nonionic surfactants and/or N-vinyllactam polymers are used.
  • Nonionic surfactants there are polyhydric alcohol types in which polyhydric alcohols and fatty acids are ester-bonded, and compounds having hydroxyl groups such as higher alcohols, alkylphenols, and propylene glycol, and alkylene oxides.
  • Known nonionic surfactants such as adduct ether type surfactants can be used, and in the present invention, at least nonionic surfactants containing alkylene oxide adducts of alcohols having 6 or more carbon atoms are included.
  • the alkylene oxide adduct of an alcohol having 6 or more carbon atoms is a compound obtained by adding an alkylene oxide to an alcohol having 6 or more carbon atoms.
  • alcohols having 6 or more carbon atoms include hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecanol, pentadecanol, hexadecanol, and heptadeca.
  • alkyl alcohols such as nol, octadecanol, nonadecanol, eicosanol, 1,2-hexanediol, 1,6-hexanediol, 1,10-decanediol; cyclohexyl alcohol, cycloheptyl alcohol, 1,4-cyclohexanedimethanol, cycloalkyl alcohols such as 1,4-cyclohexanediol; allyl alcohol; alkylphenyl alcohols such as octylphenol and nonylphenol; Of these, alkyl alcohols are preferable as the alcohol having 6 or more carbon atoms, from the viewpoints of relatively easy adjustment of the hydrophobicity depending on the structure and the addition position and environmental toxicity.
  • the above alkyl alcohol may be linear or branched.
  • the carbon number of the alcohol is preferably 10 or more, preferably 20 or less, and more preferably 18 or less.
  • the alcohol having 6 or more carbon atoms is preferably a secondary or tertiary alcohol, more preferably a secondary alcohol, in that it can achieve both high penetrating power to the solid residue interface and metal corrosion inhibition performance.
  • the alcohol having 6 or more carbon atoms may be monovalent, divalent, or polyvalent, but monovalent alcohol is preferable from the viewpoint of ease of production and cost.
  • alkylene oxide to be added to the alcohol having 6 or more carbon atoms examples include ethylene oxide, propylene oxide, butylene oxide, etc. Among them, at least one selected from the group consisting of ethylene oxide and propylene oxide is preferable, A mixed type of ethylene oxide and propylene oxide is more preferred.
  • alkylene oxide adducts of alcohols having 6 or more carbon atoms examples include primary alcohol ethoxylate, secondary alcohol ethoxylate, tertiary alcohol ethoxylate, octylphenyl ethoxylate, nonylphenyl ethoxylate, benzylphenyl ethoxylate, and acetylene.
  • ethoxylate Primary alcohol ethoxylate, acetylenic primary dialcohol ethoxylate, acetylenic secondary alcohol ethoxylate, acetylenic secondary dialcohol ethoxylate, acetylenic tertiary alcohol ethoxylate, acetylenic tertiary dialcohol ethoxylate, etc. be done.
  • the above ethoxylates are those to which at least ethylene oxide (EO) is added, and those to which ethylene oxide (EO) and other alkylene oxides (eg, propylene oxide (PO)) are added are also included.
  • the alkylene oxide adduct of the alcohol having 6 or more carbon atoms preferably has a clouding point of 25° C. or higher, and a clouding point of 40° C. or higher, because it can form a uniform solution without separating in the detergent composition. is more preferable.
  • the above cloud point can be obtained by a method of lowering the temperature of a 1% aqueous solution of a nonionic surfactant while stirring and monitoring the temperature, and observing the temperature at which the solution becomes transparent visually.
  • nonionic surfactant examples include, for example, a polyalkylene oxide alkyl ether surfactant, a block polymer system composed of polyethylene oxide and polypropylene oxide, a polyalkylene oxide alkylphenyl ether surfactant, polyoxy Alkylene distyrenated phenyl ether-based surfactants, polyalkylene tribenzylphenyl ether-based surfactants, acetylene polyalkylene oxide-based surfactants, and the like are included.
  • polyalkylene oxide alkyl ether-based surfactants and block polymer-based surfactants composed of polyethylene oxide and polypropylene oxide are preferable because they can suppress corrosion of the metal laminated film due to the detergent composition.
  • the alkylene oxide adduct of alcohol having 6 or more carbon atoms is preferably a compound represented by the following general formula (2) or (3).
  • R 6 , R 7 and R 8 are the same or different and represent a hydrogen atom or an alkyl group.
  • R 9 and R 10 are the same or different and represent an alkylene group.
  • x and y are the same or different and represent an integer of 0 to 50.
  • (x+y) is an integer of 1 or more.
  • R 11 , R 12 , R 13 and R 14 are the same or different and represent a hydrogen atom or an alkyl group.
  • R 15 , R 16 , R 17 , R 18 and R 19 are the same or different and represent an alkylene group or an alkynylene group.
  • x and y are the same or different and represent an integer of 0 to 50; (x+y) is an integer of 1 or more. )
  • the alkyl groups represented by R 6 , R 7 and R 8 may be linear or branched.
  • the number of carbon atoms in the alkyl group is preferably 1-20, more preferably 1-18, even more preferably 1-16.
  • Examples of the alkyl group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, sec-butyl group, iso-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2 , 2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group,
  • R 6 , R 7 and R 8 are preferably alkyl groups in that the molecular structure is compact and high permeability can be exhibited.
  • the total number of carbon atoms in R 6 , R 7 and R 8 is preferably 5 to 19, more preferably 7 to 17, even more preferably 9 to 15.
  • 11-13 is most preferred.
  • the alkylene group represented by R 9 and R 10 may be linear or branched.
  • the alkylene group include methylene group, ethylene group, n-propylene group, 2-propylene group, n-butylene group, pentamethylene group, hexamethylene group, neopentylene group, heptamethylene group, octamethylene group and nonamethylene group.
  • decamethylene group methylmethylene group, methylethylene group, 1-methylpentylene group, 1,4-dimethylbutylene group and the like.
  • an alkylene group having 2 or 3 carbon atoms is preferable in terms of ease of production and ability to control hydrophilicity and hydrophobicity.
  • —(R 9 O) x (R 10 O) y H is —(CH 2 CH 2 O) x H, -(CH 2 CH 2 O) x (CH 2 CH(CH 3 )O) y H, preferably -(CH 2 CH 2 O) x (CH 2 CH(CH 3 ) O) yH is more preferred.
  • x and y are the same or different and are an integer of 0 to 50, preferably an integer of 0 to 30, more preferably an integer of 0 to 24, 0 An integer of ⁇ 16 is even more preferred.
  • x represents the average number of added moles of alkylene oxide (R 9 O)
  • y represents the average number of added moles of alkylene oxide (R 10 O).
  • x and y may be the same or different in any alkylene oxide.
  • x is preferably an integer of 1-20, more preferably an integer of 3-18, even more preferably an integer of 5-16.
  • y is preferably an integer of 0-20, more preferably an integer of 0-15, even more preferably an integer of 1-10.
  • (x+y) is an integer of 1 or more. That is, at least one of x and y is an integer of 1 or more.
  • (x+y) is preferably an integer of 1-50, more preferably an integer of 3-30.
  • the alkyl groups represented by R 11 , R 12 , R 13 and R 14 are the same as the alkyl groups represented by R 6 , R 7 and R 8 described above. be done.
  • the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and a tert-butyl group in that the molecular structure becomes compact and high permeability can be expressed.
  • sec-butyl or iso-butyl groups are preferred.
  • the total number of carbon atoms of R 11 , R 12 , R 13 and R 14 is preferably 5 to 20 from the viewpoint of the balance between hydrophilicity and hydrophobicity of the surfactant, It is more preferably 6-16, and even more preferably 8-12.
  • examples of the alkylene group represented by R 15 , R 16 , R 17 , R 18 and R 19 include the same alkylene groups represented by R 9 and R 10 described above. be done. Among them, R 15 , R 16 , R 17 and R 18 are preferably an alkylene group, more preferably an alkylene group having 2 or 2 carbon atoms.
  • examples of the alkynylene group represented by R 15 , R 16 , R 17 , R 18 and R 19 include an ethynylene group (-C ⁇ C-), a propynylene group (-C ⁇ C —CH 2 —), 1-butynylene group (—C ⁇ C—CH 2 —CH 2 —), 2-butynylene group (—CH 2 —C ⁇ C—CH 2 —), and the like.
  • R 19 is preferably an alkynylene group, more preferably an ethynylene group, a propynylene group, a 1-butynylene group, or a 2-butynylene group, and an alkynylene group having 2 or 3 carbon atoms. is more preferred, and an alkylene group having 2 carbon atoms is most preferred.
  • —(R 15 O) x (R 16 O) y —H and —(R 17 O) x (R 18 O) y —H are the above-mentioned —(R 9 O ) x (R 10 O) y H and the same groups are preferably mentioned.
  • x and y are the same or different and are an integer of 0 to 50, preferably an integer of 0 to 30, more preferably an integer of 0 to 24, 0 An integer of 0 to 20 is more preferred, an integer of 0 to 16 is even more preferred, an integer of 0 to 15 is particularly preferred, and an integer of 0 to 10 is most preferred.
  • x represents the average number of added moles of alkylene oxide (R 15 O) and (R 17 O)
  • y represents the average number of added moles of alkylene oxide (R 16 O) and (R 18 O).
  • x and y may be the same or different in any alkylene oxide.
  • x is preferably an integer of 1-20, more preferably an integer of 1-12, and even more preferably an integer of 2-8.
  • y is preferably an integer of 0 to 20, more preferably an integer of 0 to 10, still more preferably an integer of 0 to 8, and even more preferably an integer of 0 to 5 .
  • (x+y) is an integer of 1 or more. That is, at least one of x and y is an integer of 1 or more.
  • (x+y) is preferably an integer of 1-50, more preferably an integer of 2-30, and even more preferably an integer of 3-30.
  • N-Vinyllactam Polymer The N-vinyllactam polymer is obtained by polymerizing a monomer component containing an N-vinyllactam monomer which is a monomer having a lactam ring. It is a polymer that can be Specific examples of the N-vinyllactam monomers include N-vinylpyrrolidone, N-vinylcaprolactam, 3-methyl-N-vinylpyrrolidone, 4-methyl-N-vinylpyrrolidone, 5-methyl-N -vinylpyrrolidone, N-vinylpiperidone, 1-(2-propenyl)-2-pyrrolidone, N-vinyl-4-butylpyrrolidone, N-vinyl-4-propylpyrrolidone, N-vinyl-4-ethylpyrrolidone, N-vinyl -4-methylpyrrolidone, N-vinyl-4-methyl-5-ethylpyrroli
  • the weight average molecular weight of the N-vinyllactam polymer is preferably 500 to 50,000, more preferably 1,000 to 40,000, even more preferably 2,000 to 30,000.
  • the weight average molecular weight can be obtained by measuring by a gel permeation chromatography (GPC) method (in terms of PEO).
  • the above nonionic surfactant and N-vinyllactam polymer may be used alone or in combination of two or more.
  • the content of the compound (1A) (component (1A)) is preferably 0.5 to 65% by mass with respect to 100% by mass of the active ingredient in the first post-CMP step cleaning composition. , more preferably 1 to 60% by mass, even more preferably 2 to 55% by mass.
  • active ingredient refers to all ingredients other than the solvent in the post-cleaning composition for the CMP process.
  • the content of the compound (1A) (component (1A)) is preferably 0.001 to 5% by mass with respect to 100% by mass of the first post-CMP step cleaning composition. 005 to 2% by mass, and even more preferably 0.01 to 1% by mass.
  • the first post-cleaning composition for the CMP step contains aliphatic amines (hereinafter also referred to as “aliphatic amines (1B)” or “component (1B)”). .
  • aliphatic amines (1B) aliphatic amines
  • component (1B) component
  • Examples of the aliphatic amines (1B) include primary aliphatic amines, secondary aliphatic amines, and tertiary aliphatic amines.
  • the aliphatic amines (1B) preferably contain an amine compound represented by the following general formula (1) and/or a polyalkyleneimine.
  • R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, an alkyl group, or —R 4 —(NH—R 5 ) n —NH 2.
  • R 4 and R 5 is the same or different and represents an alkylene group having 1 to 6 carbon atoms, and n represents an integer of 0 to 100.
  • R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, an alkyl group, or —R 4 —(NH—R 5 ) n —NH 2 .
  • the number of carbon atoms in the alkyl group represented by R 1 , R 2 and R 3 is preferably 1 to 6, more preferably 1 to 5, and 1 to 4, from the viewpoint of water solubility. is more preferred.
  • n --NH 2 represented by R 1 , R 2 and R 3 , R 4 and R 5 are the same or different and represent an alkylene group having 1 to 6 carbon atoms. . Also, n represents an integer of 0-100. n represents the number of repetitions of -(NH-R 5 )-, preferably an integer of 0 to 50, more preferably an integer of 0 to 30, still more preferably an integer of 0 to 20, particularly preferably Represents an integer from 0 to 10.
  • Specific examples of the compound represented by the general formula (1) include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, diethylenetriamine, N-ethylbutylamine, 1,2-bis-(3 -aminopropylamino)ethane, tributylamine, 3-(diethylamino)propylamine, triethylenetetramine, tetraethylenepentamine and the like.
  • polyalkyleneimine examples include polyethyleneimine, polypropyleneimine, polybutyleneimine, polypentyleneimine, and the like.
  • the above polyalkyleneimine may be linear or branched. Among them, a branched shape is preferable in terms of ease of production.
  • the molecular weight of the aliphatic amines (1B) is preferably 2000 or less. When the molecular weight is 2000 or less, the viscosity of the post-cleaning composition for the CMP process is favorable.
  • the molecular weight of the aliphatic amines is more preferably 300 or less, still more preferably 250 or less, and even more preferably 220 or less.
  • the molecular weight of the above-mentioned aliphatic amine (1B) is preferably 50 or more because of its low boiling point.
  • the aliphatic amines (1B) may be used alone or in combination of two or more.
  • the content of the aliphatic amine (1B) (component (1B)) is 30 to 95% by mass with respect to 100% by mass of the active ingredients in the first post-CMP step cleaning composition. It is preferably from 35 to 93% by mass, and even more preferably from 40 to 90% by mass.
  • the content of the aliphatic amine (1B) (component (1B)) is preferably 0.01 to 5% by mass with respect to 100% by mass of the first post-cleaning composition for the CMP step. , more preferably 0.05 to 2% by mass, and even more preferably 0.1 to 1% by mass.
  • the post-cleaning composition for the first CMP step contains a corrosion inhibitor (hereinafter also referred to as “corrosion inhibitor (1C)” or “component (1C)”), As an inhibitor, at least one selected from the group consisting of nitrogen-containing heterocyclic compounds and carboxylate compounds is included.
  • a corrosion inhibitor hereinafter also referred to as “corrosion inhibitor (1C)” or “component (1C)
  • As an inhibitor at least one selected from the group consisting of nitrogen-containing heterocyclic compounds and carboxylate compounds is included.
  • the nitrogen-containing heterocyclic compound is not particularly limited as long as it is a compound having a heterocyclic ring having at least one nitrogen atom. It may contain atoms.
  • the nitrogen-containing heterocyclic ring may be either saturated or unsaturated, but is preferably a nitrogen-containing unsaturated heterocyclic ring in terms of high adsorption performance with respect to the transition metal film.
  • the above nitrogen-containing heterocyclic compound may be a heteromonocyclic compound or a condensed heterocyclic compound.
  • heteromonocyclic compounds include five-membered ring compounds such as pyrrole, pyrazoline, pyrazole, imidazole, triazole, imidazoline, oxazoline, oxazole, and isoxazole; piperidine, pyridine, pyrazine, piperazine, pyrimidine, pyridazine, triazine, morpholine 6-membered ring compounds such as; and derivatives thereof.
  • five-membered ring compounds such as pyrrole, pyrazoline, pyrazole, imidazole, triazole, imidazoline, oxazoline, oxazole, and isoxazole
  • piperidine pyridine, pyrazine, piperazine, pyrimidine, pyridazine, triazine, morpholine 6-membered ring compounds such as; and derivatives thereof.
  • Examples of the derivative include compounds in which at least one atom in the nitrogen-containing heterocyclic ring is substituted with an alkyl group, an aryl group, an amino group, a carboxyl group, a hydroxy group, a ketone group, or a group combining these. be done.
  • heteromonocyclic compounds include 1H-pyrrole, 1-pyrroline, 2-pyrroline, 3-pyrroline, pyrrolidine, pyrrolidone, ⁇ -butyrolactam, ⁇ -valerolactam, proline, prolyl, 1H-pyrazole, 1-pyrazoline, 2-pyrazoline, pyrazolidine, pyrarizolidone, 3-pyrazolone, 4-pyrazolone, 5-pyrazolone, 1H-pyrazole-4-carboxylic acid, ethyl pyrazole-4-carboxylate, 1-methyl-1H-pyrazole-5 -carboxylic acid, 5-methyl-1H-pyrazole-3-carboxylic acid, 3,5-pyrazoledicarboxylic acid, 3-amino-5-hydroxypyrazole, 1H-imidazole, 2-imidazoline, 3-imidazoline, 4-imidazoline, imidazolidine, imidazolidone, ethyleneurea, hydantoin, all
  • condensed heterocyclic compound examples include indole, isoindole, benzimidazole, benzotriazole, triazine, quinoline, isoquinoline, quinazoline, purine, cinnoline, phthalazine, quinoxaline, acridine, phenanthridine, and derivatives thereof. be done.
  • condensed heterocyclic compound examples include benzotriazole and uric acid.
  • the nitrogen-containing heterocyclic compound may contain at least one selected from the group consisting of pyrrole, pyridine, triazole, triazine, purine, and derivatives thereof, because of its high adsorption performance to transition metal films.
  • Uric acid, nicotinic acid, triazole, or melamine is more preferred, and uric acid is even more preferred.
  • the above nitrogen-containing heterocyclic compounds may be used alone or in combination of two or more.
  • the carboxylate compound is not particularly limited as long as it is a salt of a compound having a carboxy group, but fatty acid salts are preferred.
  • the fatty acid salt may be either a saturated fatty acid salt or an unsaturated fatty acid salt.
  • the number of carbon atoms in the fatty acid salt is preferably 6 to 50, more preferably 8 to 40, even more preferably 10 to 30, from the viewpoint of improving the corrosion resistance of the adsorbed metal film. , 14-24.
  • fatty acid salts include saturated butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, and arachidic acid.
  • Salts of fatty acids salts of unsaturated fatty acids such as crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, eicosenoic acid, linoleic acid and linolenic acid.
  • the fatty acid salts improve the corrosion resistance of the adsorbed metal film, and include capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, stearic acid, arachidic acid, myristoleic acid, It is preferably a salt of at least one fatty acid selected from the group consisting of palmitoleic acid, oleic acid, eicosenoic acid, linoleic acid and linolenic acid.
  • Examples of the above salts include alkali metal salts such as potassium salts and cesium salts; alkaline earth metal salts such as magnesium salts, calcium salts, strontium salts and barium salts; ammonium salts; quaternary ammonium salts; Examples include organic amine salts such as salts. Among these salts, alkali metal salts, ammonium salts, quaternary ammonium salts and organic amine salts are preferred, alkali metal salts and ammonium salts are more preferred, and potassium salts and ammonium salts are even more preferred.
  • the carboxylate compound is palmitate, stearate, arachidate, palmitoleate, oleate, or eicosenoic acid from the viewpoint of improving corrosion resistance due to the balance of polar groups and hydrophobic groups. It is preferably a salt, more preferably an alkali metal salt or ammonium salt of palmitic acid, stearic acid, arachidic acid, palmitoleic acid, oleic acid or eicosenoic acid, and even more preferably an alkali metal salt of oleic acid. , and potassium oleate.
  • the above carboxylate compounds may be used alone or in combination of two or more.
  • the post-cleaning composition for the first CMP step may further contain other corrosion inhibitors in addition to the nitrogen-containing heterocyclic compound and the carboxylate compound.
  • Other corrosion inhibitors include known corrosion inhibitors such as rust inhibitors and anticorrosive agents.
  • Specific examples of the corrosion inhibitor include oxide-coated corrosion inhibitors such as chromates, molybdates, tungstates, and nitrites; precipitation of polymerized phosphates, zinc salts, sulfur-containing organic compounds, and the like; Coating type corrosion inhibitors, adsorption coating type corrosion inhibitors such as alkanolamines, alkyleneamine ethylene oxide adducts, alkyl phosphate ester salts, various surfactants, and the like can be mentioned.
  • the total content of (1C-1) nitrogen-containing heterocyclic compound and (1C-2) carboxylate compound in the corrosion inhibitor is 50% by mass or more with respect to 100% by mass of the total amount of corrosion inhibitor. It is preferably 55% by mass or more, more preferably 60% by mass or more, and particularly preferably 100% by mass.
  • the content ratio [(1C-1)/(1C-2)] of (1C-1) nitrogen-containing heterocyclic compound and (1C-2) carboxylate compound is 0/100 to 100 in mass ratio. /0 is preferable, and either compound may be used alone or may be used by mixing at any ratio.
  • the content of the corrosion inhibitor (1C) is 0.2 to 35% by mass with respect to 100% by mass of the active ingredients in the first post-CMP step cleaning composition. is preferred, 0.5 to 30 mass % is more preferred, and 1 to 25 mass % is even more preferred.
  • the content of the corrosion inhibitor (1C) is preferably 0.001 to 3% by mass with respect to 100% by mass of the first post-CMP step cleaning composition. It is more preferably 0.003 to 2% by mass, even more preferably 0.005 to 1% by mass.
  • the first post-cleaning composition for the CMP process of the present invention may include other optional components (1D) in addition to the components (1A), (1B), and (1C) described above. may contain Examples of the component (1D) include pH adjusters, chelating agents, solvents, surfactants, and the like.
  • the pH adjuster is not particularly limited as long as it is a component capable of adjusting the pH to a target, and examples thereof include acid compounds and alkali compounds.
  • the acid compound include inorganic acids such as sulfuric acid and nitric acid and salts thereof, and organic acids such as acetic acid and lactic acid and salts thereof.
  • the alkali compound include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and cesium hydroxide; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and monoisopropanolamine; tetramethylammonium hydroxide.
  • tetraethylammonium hydroxide tetrapropylammonium hydroxide, trimethyl-2-hydroxyethylammonium hydroxide (choline), triethyl(hydroxyethyl)ammonium hydroxide and the like; quaternary ammonium salts;
  • the above pH adjusters may be used alone or in combination of two or more.
  • the chelating agent examples include oxalic acid, citric acid, tartaric acid, malic acid, picolinic acid, glycine and the like.
  • Phosphonic acid chelating agents such as N,N,N',N'-ethylenediaminetetrakis (methylene phosphonic acid), glycine-N,N-bis (methylene phosphonic acid), nitrilotris (methylene phosphonic acid) and the like can also be mentioned.
  • sulfur-containing amino acids such as cysteine and methionine are preferably used as the chelating agent.
  • the above chelating agents may be used alone or in combination of two or more.
  • the solvent examples include water, aprotic polar organic solvents such as water, N-methyl-2-pyrrolidinone, N,N-dimethylacetamide and dimethylsulfoxide, protic organic solvents such as lower alcohols, aromatic alcohols and glycols. is mentioned. Especially, it is preferable that the said solvent contains water.
  • the solvent may be a mixed liquid containing two or more kinds.
  • surfactant examples include anionic surfactants and cationic surfactants other than the nonionic surfactants described above.
  • anionic surfactant examples include aliphatic monocarboxylates, polyoxyethylene alkyl ether carboxylates, N-acylsarcosine salts, N-acylglutamate carboxylate anionic surfactants; dialkyl sulfosuccinates; sulfonate type anions such as acid salts, alkanesulfonates, alpha-olefinsulfonates, alkylbenzenesulfonates, naphthalenesulfonates-formaldehyde condensates, alkylnaphthalenesulfonates, N-methyl-N-acyl taurates, etc.
  • Surfactants sulfuric acid ester type anionic surfactants such as alkyl sulfates, polyoxyethylene alkyl ether sulfates, oil sulfates; and alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene Phosphate ester type anionic surfactants of alkylphenyl ether phosphates can be mentioned.
  • cationic surfactant examples include alkylamine salt-type cationic surfactants such as monoalkylamine salts, dialkylamine salts, and trialkylamine salts; and dialkyldimethylammonium chloride, dialkyldimethylammonium bromide, dialkyldimethyl Quaternary ammonium salt type cationic surfactants such as ammonium iodide, alkyltrimethylammonium chloride, alkyltrimethylammonium bromide, alkyltrimethylammonium iodide, alkylbenzyldimethylammonium chloride and the like.
  • alkylamine salt-type cationic surfactants such as monoalkylamine salts, dialkylamine salts, and trialkylamine salts
  • dialkyldimethylammonium chloride dialkyldimethylammonium bromide
  • dialkyldimethyl Quaternary ammonium salt type cationic surfactants such as ammonium io
  • the first post-CMP cleaning composition is preferably an aqueous solution having a pH (hydrogen ion concentration) of 7.5 or higher at 25°C.
  • the pH (25°C) of the first post-CMP cleaning composition is preferably 8.0 or higher, still more preferably 8.5 or higher, and even more preferably 10.0 or higher.
  • the pH of the first post-CMP cleaning composition can be adjusted by adjusting the content of the alkali compound described above. The above pH can be determined using a pH meter (eg, F71S, manufactured by Horiba Ltd.).
  • the first post-CMP cleaning composition preferably has a corrosion current value of 10 ⁇ A/cm 2 or less and a corrosion potential difference at the interface of dissimilar metals of 60 mV or less. When the corrosion current value and the corrosion potential difference are within the above ranges, corrosion of the substrate to be cleaned can be suppressed. More preferably, the first post-CMP cleaning composition has a corrosion current value of 5 ⁇ A/cm 2 or less and a corrosion potential difference at the interface of different metals of 30 mV or less.
  • the corrosion potential difference at the dissimilar metal interface is 2 or less and the corrosion potential difference at the dissimilar metal interface is 25 mV or less, and it is particularly preferable that the corrosion current value is 1 ⁇ A/cm 2 or less and the dissimilar metal interface corrosion potential difference is 20 mV or less.
  • the corrosion current value and the corrosion potential difference can be obtained by measuring by the method described in Examples below.
  • the second post-CMP cleaning composition of the present invention contains the three specific components (2A), (2B), and (2C) described above, thereby removing metal residue and organic residue from the wafer surface. Excellent removal and adhesion prevention, and excellent corrosion control. In particular, when ceria is used as abrasive grains to clean the surface of a wafer subjected to a CMP process, the effect is further exhibited. In addition, the second post-CMP cleaning composition of the present invention exhibits the above effects even more when used for cleaning the surface of a film containing silicon oxide and/or silicon nitride in a semiconductor manufacturing process. .
  • the second post-CMP cleaning composition is excellent in removing and preventing adhesion of metal residue, ceria abrasive residue and organic residue, and is also excellent in corrosion inhibition, because of the second post-CMP step cleaning composition.
  • the nonionic surfactant and/or N-vinyllactam polymer contained in the cleaning composition permeate the substrate surface and the interface between the abrasive residue and dirt, and float in water, which is the main component of the cleaning liquid, while the organic acid compound It is presumed that the contaminants can be removed from the substrate surface by cutting the covalent bond formed at the interface between the contaminants and the substrate by the pH adjuster, the oxidizing agent, or the like.
  • the adsorption of organic acid compounds, nonionic surfactants, and/or N-vinyllactam polymers on the surface of the deposited metal film that appears after the CMP process causes an electrochemical reaction between chemical components coexisting in the cleaning solution. It is presumed that the corrosion potential and the corrosion current value of the metal species constituting the deposited metal film can be reduced by setting the interaction to an equilibrium state.
  • the post-cleaning composition for the second CMP step comprises a nonionic surfactant having an aliphatic alcohol alkylene oxide adduct structure, and , and N-vinyllactam polymers (hereinafter also referred to as "compound (2A)” or “component (2A)”).
  • compound (2A) or “component (2A)”
  • the alkylene oxide adduct structure of the fatty alcohol is a structure in which an alkylene oxide is added to the fatty alcohol.
  • aliphatic alcohol examples include methanol, ethanol, propanol, isopropanol, butanol, isobutyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetra decanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, methanediol, ethylene glycol, 1,4-butanediol, 1,2-hexanediol, 1,6-hexanediol, Alkyl alcohols such as 1,10-decanediol; cycloalkyl alcohols such as cyclopentyl alcohol, cyclohexyl alcohol, cycloheptyl
  • the number of carbon atoms in the aliphatic alcohol is preferably 6 or more, more preferably 10 or more.
  • the number of carbon atoms in the alcohol is preferably 18 or less, more preferably 16 or less.
  • the above-mentioned aliphatic alcohol is preferably a secondary or tertiary alcohol, more preferably a secondary alcohol, in terms of high penetrating power to the solid residue interface and excellent suppression of metal corrosion.
  • the aliphatic alcohol is preferably a secondary or tertiary alkyl alcohol having 6 or more carbon atoms.
  • the aliphatic alcohol may be monohydric, dihydric, or polyhydric, but monohydric alcohols are preferred in terms of ease of production and cost.
  • alkylene oxide added to the aliphatic alcohol examples include ethylene oxide, propylene oxide and butylene oxide. Among them, at least one selected from the group consisting of ethylene oxide and propylene oxide is preferable, and a mixed type of ethylene oxide and propylene oxide is more preferable.
  • the alkylene oxide adduct structure of the fatty alcohol preferably contains two or more alkylene oxides.
  • the alkylene oxide adduct structure of the aliphatic alcohol has an alkylene oxide adduct structure of an alcohol having 6 or more carbon atoms, and preferably includes block polymer structures of two or more alkylene oxides.
  • alkylene oxide adduct structure of the aliphatic alcohol examples include primary alcohol ethoxylate, secondary alcohol ethoxylate, tertiary alcohol ethoxylate, acetylenic primary alcohol ethoxylate, acetylenic primary dialcohol ethoxylate, acetylenic di-alcohol ethoxylate, Examples include primary alcohol ethoxylates, acetylenic secondary dialcohol ethoxylates, acetylenic tertiary alcohol ethoxylates, acetylenic tertiary dialcohol ethoxylates, and the like.
  • the above ethoxylates are those to which at least ethylene oxide (EO) is added, and those to which ethylene oxide (EO) and other alkylene oxides (eg, propylene oxide (PO)) are added are also included.
  • the alkylene oxide adduct structure of the above-mentioned aliphatic alcohol preferably has a clouding point of 25° C. or higher, more preferably 40° C. or higher, in that a uniform solution can be formed without separating in the detergent composition. is more preferable.
  • the above cloud point can be obtained by a method of lowering the temperature of a 1% aqueous solution of a nonionic surfactant while stirring and monitoring the temperature, and observing the temperature at which the solution becomes transparent visually.
  • nonionic surfactant (2A-1) examples include, for example, a polyalkylene oxide alkyl ether surfactant, a block polymer system composed of polyethylene oxide and polypropylene oxide, and an acetylene polyalkylene oxide surfactant. agents and the like.
  • polyalkylene oxide alkyl ether-based surfactants and block polymer-based surfactants composed of polyethylene oxide and polypropylene oxide are preferable because they can suppress corrosion of the metal laminated film due to the detergent composition.
  • the nonionic surfactant (2A-1) is represented by general formula (2) or (3) described in the section “Compound (1A)” of the first post-cleaning composition for the CMP step. Compounds similar to the represented compounds are more preferred.
  • N-Vinyllactam Polymer As the N-vinyllactam polymer (2A-2), the same compounds as the above N-vinyllactam polymer (1A-2) can be mentioned. Among them, polyvinylpyrrolidone obtained by polymerizing a monomer component containing N-vinylpyrrolidone is preferable as the N-vinyllactam polymer (2A-2).
  • the weight average molecular weight of the N-vinyllactam polymer (2A-2) is preferably 500 to 50,000, more preferably 1,000 to 40,000, even more preferably 2,000 to 30,000.
  • the weight average molecular weight can be obtained by measuring by a gel permeation chromatography (GPC) method (in terms of PEO).
  • the above nonionic surfactant and N-vinyllactam polymer may be used alone or in combination of two or more.
  • the content of the compound (2A) (component (2A)) is preferably 0.005 to 3% by mass with respect to 100% by mass of the second post-CMP step cleaning composition. It is more preferably from 01 to 1% by mass, and even more preferably from 0.1 to 0.5% by mass.
  • the second post-CMP cleaning composition preferably contains an organic acid compound (hereinafter also referred to as “organic acid compound (2B)” or “component (2B)”). .
  • organic acid compound By further including the organic acid compound, it is believed that the organic acid compound can break the covalent bond formed at the interface between the contaminant and the substrate and remove the contaminant from the substrate surface.
  • the adsorption of the organic acid compound on the surface of the deposited metal film that appears after the CMP process brings the electrochemical interaction between the chemical components coexisting in the cleaning solution into an equilibrium state, and the metal species that compose the deposited metal film are eliminated. It is thought that the corrosion potential and corrosion current value can be reduced.
  • organic acid compound (2B) examples include carboxylic acid compounds, ascorbic acid, phenol compounds, phosphonic acids, boronic acids, and the like.
  • carboxylic acid compounds and ascorbic acid are preferable in that organic acid compound residues can be easily removed by rinsing with pure water or alcohol after the process, and the adverse effect on the next process can be minimized. more preferred.
  • carboxylic acid compound examples include organic acid compounds having a carboxyl group. , monocarboxylic acid compounds such as stearic acid; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, gluconic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, 5-norbornene dicarboxylic acid acid compounds; tricarboxylic acid compounds such as citric acid; aspartic acid, glutamic acid, glycine, alanine, phenylalanine, leucine, isoleucine, cysteine, methionine, tyrosine, valine, threonine, serine, proline, tryptophan, asparagine, glutamine, lysine, arginine, amino acids such as histidine; aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and propyl
  • the carboxylic acid compound is preferably a dicarboxylic acid compound, a tricarboxylic acid compound, an aminopolycarboxylic acid, more preferably citric acid, oxalic acid, 5-norbornene dicarboxylic acid, ethylenediaminetetraacetic acid, citric acid, Acids, oxalic acid, 5-norbornenedicarboxylic acid, and ethylenediaminetetraacetic acid are more preferred.
  • the above organic acid compounds may be used alone or in combination of two or more.
  • the content of the organic acid compound (2B) (component (2B)) is preferably 0.05 to 10% by mass with respect to 100% by mass of the second post-CMP step cleaning composition. It is more preferably 0.1 to 7% by mass, even more preferably 0.5 to 4% by mass.
  • the post-cleaning composition for the second CMP step contains a pH adjuster (hereinafter also referred to as “pH adjuster (2C)” or “component (2C)”), It can improve the stability of chemical species in the unoxidized state in water.
  • the pH adjuster (2C) used in the second aspect of the present invention is not particularly limited as long as it is a compound capable of adjusting the pH to a desired value, and examples thereof include known acidic compounds and basic compounds.
  • the pH adjuster (2C) is preferably a basic pH adjuster because it can suppress the generation of oxygen due to the decomposition of water and the generation of hydrogen due to dissolution of the metal component in the cleaning liquid.
  • Examples of the acidic compound include nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, and boric acid.
  • Examples of the basic compound include inorganic hydroxides such as sodium hydroxide and potassium hydroxide; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and monoisopropanolamine; methylamine, dimethylamine, trimethylamine; Alkylamines such as ethylamine, diethylamine, triethylamine, ethylenediamine, N,N-diisopropylethylamine, tetramethylethylenediamine, and hexamethylenediamine; aromatic amines such as aniline and toluidine; and nitrogen-containing complexes such as pyrrole, pyridine, picoline, and lutidine.
  • alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and monoisopropanolamine
  • methylamine dimethylamine, trimethylamine
  • Alkylamines such as ethylamine, diethylamine, triethylamine, ethylenediamine, N
  • organic amines such as cyclic compounds; salts of the above-mentioned organic amines (organic amine salts); tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, trimethyl-2-hydroxyethylammonium hydroxide (choline), quaternary ammonium salts such as triethyl(hydroxyethyl)ammonium hydroxide and dimethylbis(2-hydroxyethyl)ammonium hydroxide; ammonium salts such as ammonium carbonate, ammonium hydrogencarbonate and ammonium carbamate; and ammonia.
  • hydroxides, organic amines, organic amine salts, quaternary ammonium salts, and ammonium salts are preferable because etching of the film surface containing silicon oxide and/or silicon nitride can be suppressed, and hydroxides, organic amines, Quaternary ammonium salts and ammonium salts are more preferred.
  • the pH adjuster (2C) may be used alone or in combination of two or more.
  • the content of the pH adjuster (2C) (component (2C)) is preferably 0.01 to 15% by mass with respect to 100% by mass of the second post-CMP step cleaning composition. It is more preferably 0.1 to 10% by mass, even more preferably 0.5 to 5% by mass.
  • the second post-CMP cleaning composition may further contain an oxidizing agent, but preferably does not contain an oxidizing agent from the viewpoint of suppressing metal corrosion.
  • the oxidizing agent (2D) include hydrogen peroxide, ozone, nitric acid, nitrous acid, persulfuric acid, dichromic acid, permanganic acid, and salts thereof. Among them, hydrogen peroxide is preferable from the viewpoint of easy availability of high-purity products required in the field of semiconductors and ease of disposal.
  • the content of the oxidizing agent (2D) (component (2D)) is preferably 1.0% by mass or less with respect to 100% by mass of the second post-CMP step cleaning composition.
  • the content of the oxidizing agent is more preferably 0.5% by mass or less with respect to 100% by mass of the second post-CMP cleaning composition, from the viewpoint of causing corrosion of the metal film. It is preferably 0.1% by mass or less, even more preferably 0.05% by mass or less, particularly preferably 0.03% by mass or less, and most preferably 0% by mass. preferable.
  • the post-cleaning composition for the second CMP process may optionally contain other components in addition to the components (2A), (2B), (2C) and (2D) described above.
  • Component (2E) may also be included.
  • examples of the other component (2E) include solvents, chelating agents, anionic surfactants, cationic surfactants, corrosion inhibitors, and the like. These contents can be set appropriately.
  • solvents used in the second post-CMP cleaning composition include water, aprotic polar organic solvents such as N-methyl-2-pyrrolidinone, N,N-dimethylacetamide, and dimethylsulfoxide; Examples include protic organic solvents such as lower alcohols, aromatic alcohols and glycols. Especially, it is preferable that the said solvent contains water.
  • the solvent may be a mixed liquid or the like containing water and another solvent such as alcohol.
  • One of the above solvents may be used alone, or two or more thereof may be used in combination.
  • Examples of the chelating agent used in the second post-cleaning composition for the CMP step include N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid), glycine-N,N-bis(methylene phosphonic acid), phosphonic acid-based chelating agents such as nitrilotris (methylene phosphonic acid), thiol-based chelating agents such as methanethiol, thiophenol, glutathione, triphenylphosphine, 1,2-bis(diphenylphosphino)ethane, etc. mentioned.
  • the above chelating agents may be used alone or in combination of two or more.
  • anionic surfactant and the cationic surfactant used in the second post-cleaning composition for the CMP process are described in the section on the post-cleaning composition for the first CMP process.
  • An anionic surfactant similar to the cationic surfactant, an anionic surfactant similar to the cationic surfactant, and a cationic surfactant are described in the section on the post-cleaning composition for the first CMP process.
  • corrosion inhibitors used in the second post-CMP process cleaning composition include nitrogen-containing organic compounds such as benzotriazole, 3-aminotriazole, trialkylamine, ammonia, uric acid, melamine, urea and thiourea.
  • the corrosion inhibitor is preferably a benzotriazole-based compound, and particularly preferably benzotriazole.
  • the second post-CMP cleaning composition is preferably an aqueous solution having a pH (hydrogen ion concentration) of 7.5 or higher at 25°C.
  • the pH (25° C.) of the second post-CMP cleaning composition is more preferably 8.0 or higher, and even more preferably 8.5 or higher.
  • the adjustment of the pH of the second post-CMP cleaning composition can be carried out by appropriately adjusting the content of the pH adjusting agent described above.
  • the above pH can be determined using a pH meter (eg, F71S, manufactured by Horiba Ltd.).
  • the first post-cleaning composition for the CMP process of the present invention is prepared by mixing the component (1A), component (1B), component (1C), and optionally component (1D) described above. be able to.
  • the second post-CMP cleaning composition of the present invention contains the components (2A), (2B), (2C) and, if necessary, components (2D) and (2E). It can be prepared by mixing.
  • the above-mentioned mixing is not particularly limited, and can be performed by mixing/dispersing means using a known stirrer, mixer, disperser, or the like.
  • the post-CMP cleaning composition of the present invention is used in the post-CMP cleaning step in the semiconductor manufacturing process. More specifically, the post-CMP cleaning composition of the present invention is preferably used in a step of cleaning a semiconductor substrate (wafer) after a CMP step in a semiconductor manufacturing process.
  • the post-CMP cleaning method using the post-CMP cleaning composition of the present invention preferably includes the step of cleaning the surface of the semiconductor substrate after CMP using the post-CMP cleaning composition.
  • Examples of the semiconductor substrate include substrates made of silicon, silicon carbide, silicon nitride, gallium arsenide, gallium nitride, gallium phosphide, or indium phosphide.
  • the semiconductor substrate may have metal wiring, and the metal wiring includes, for example, copper wiring, tungsten wiring, aluminum wiring, cobalt wiring, ruthenium wiring, or alloy wiring of these metals and other metals. etc.
  • Other metals include metals such as tungsten, titanium, tantalum, and chromium.
  • the semiconductor substrate may include a barrier metal layer.
  • a barrier metal layer is formed to prevent diffusion of copper.
  • the barrier metal layer include layers made of tantalum, cobalt, titanium, ruthenium, and compounds containing these metals.
  • the semiconductor substrate may be anticorrosion treated.
  • the anticorrosive treatment includes a method of treating the surface of the semiconductor substrate with an anticorrosive agent.
  • the anticorrosive agent is not particularly limited, and includes compounds known as anticorrosive agents such as benzotriazoles, imidazoles, quinaldines, and quinolines.
  • an azole anticorrosive agent is preferably used because of its high anticorrosion effect.
  • azole-based anticorrosive agents examples include azole-based, triazole-based, tetrazole-based, oxazole-based, isoxazole-based, oxadiazole-based, thiazole-based, isothiazole-based, and thiadiazole-based anticorrosives.
  • the treatment method is not particularly limited, and includes known methods such as coating the surface of the semiconductor substrate with an anticorrosive agent and drying or heating to form a coating (protective film).
  • the semiconductor substrate may include an insulating film.
  • the insulating film include p-TEOS thermal oxide film, silicon nitride (SiN), silicon nitride carbide (SiCN), low dielectric constant film Low-k (SiOC, SiC), cobalt silicide (CoSi 2 ), and the like. be done.
  • polishing dust and organic residues such as the metal wiring, protective film, and insulating film described above remain on the surface of the semiconductor substrate.
  • the chemical polishing agent used in the CMP process may remain on the semiconductor substrate after the CMP process.
  • the chemical polishing agent is a slurry of abrasive grains, and metal oxides such as CeO 2 , Fe 2 O 3 , SnO 2 , MnO and SiO 2 are used as the abrasive grains. Therefore, residues of these metal oxides may exist on the surface of the semiconductor substrate after the CMP process. Further, on the surface of the semiconductor substrate, organic residues such as organometallic complexes resulting from the reaction between the metal in the slurry and the anticorrosive agent may remain on the surface of the semiconductor substrate.
  • the CMP process can be performed by a known method.
  • the post-CMP cleaning composition of the present invention is suitably used for cleaning the surface of a semiconductor substrate (wafer) after a CMP process on which the metal residue or organic residue described above is present.
  • the residue can be removed by cleaning the surface of the semiconductor substrate on which such residue is present using the post-CMP cleaning composition of the present invention.
  • it is possible to prevent the residue from redepositing on the surface of the semiconductor substrate. Furthermore, corrosion of the surface of the semiconductor substrate can be suppressed.
  • the post-CMP cleaning composition of the present invention can be suitably used for cleaning semiconductor substrates after the CMP process on which the above-mentioned metal residue and organic residue are present.
  • the first post-CMP cleaning composition of the present invention is a compound containing at least one selected from the group consisting of cobalt, copper, aluminum, ruthenium, titanium nitride, silicon nitride, and silicon oxide.
  • the second post-CMP cleaning composition of the present invention is preferably a post-CMP cleaning composition using ceria as abrasive grains.
  • the second post-CMP cleaning composition is preferably used for cleaning the surface of a film containing silicon oxide and/or silicon nitride in a semiconductor manufacturing process.
  • the post-CMP cleaning composition is particularly effective in removing the above-mentioned residues and preventing redeposition when used to clean a film surface (substrate surface) containing silicon oxide and/or silicon nitride. It can be done suitably. Furthermore, corrosion of the surface of the semiconductor substrate can be suppressed.
  • the method for cleaning the substrate (wafer) surface after CMP using the post-CMP cleaning composition of the present invention is not particularly limited, and may be performed by a known method. Wafers) may be cleaned by immersing them in the post-CMP cleaning composition, or may be cleaned by spinning, spraying, brush cleaning, or ultrasonic cleaning. Also, a batch type in which a plurality of substrates are processed at once, or a single substrate type in which substrates are processed one by one may be used.
  • the cleaning time is not particularly limited, and a conventional method may be used. 10 to 300 seconds, preferably 15 to 250 seconds.
  • the cleaning time means the contact time between the post-CMP cleaning composition and the substrate surface.
  • the temperature for the above washing is not particularly limited, and is, for example, 5 to 80.degree. C., preferably 10 to 70.degree. C., more preferably 10 to 65.degree.
  • the atmosphere is preferably an inert atmosphere in which nitrogen gas, argon gas, or the like is circulated in order to reduce dissolved oxygen in the cleaning composition.
  • Example 1 A nonionic surfactant, an aliphatic amine, and a carboxylate compound are mixed with water so as to have the formulation shown in Table 1, and then potassium hydroxide is added so that the pH (25 ° C.) becomes 11. was added to prepare the cleaning composition of Example 1.
  • the "ratio" in the table indicates the mass ratio of each component in the active ingredients (all components other than water). The obtained cleaning composition was subjected to cleaning performance evaluation and electrochemical evaluation, which will be described later.
  • Example 2 A cleaning composition was prepared in the same manner as in Example 1 so as to have the formulation shown in Table 1, and the obtained cleaning composition was subjected to cleaning performance evaluation and electrochemical evaluation.
  • electrochemical evaluation Co E CORR : -640 mV, Co I CORR : 8 ⁇ A/cm 2 , TiN E CORR : -650 mV, TiN I CORR : ND, and ⁇ E CORR at the Co/TiN interface: 10 mV.
  • Example 3 A cleaning composition was prepared in the same manner as in Example 1 so as to have the formulation shown in Table 1, and the obtained cleaning composition was subjected to cleaning performance evaluation and electrochemical evaluation.
  • electrochemical evaluation Co E CORR : -660 mV, Co I CORR : 3 ⁇ A/cm 2 , TiN E CORR : -690 mV, TiN I CORR : ND, and ⁇ E CORR at the Co/TiN interface: 30 mV.
  • Example 4 A cleaning composition was prepared in the same manner as in Example 1 so as to have the formulation shown in Table 1, and the obtained cleaning composition was subjected to cleaning performance evaluation and electrochemical evaluation.
  • electrochemical evaluation Co E CORR : -490 mV, Co I CORR : ND, TiN E CORR : -470 mV, TiN I CORR : ND, and ⁇ E CORR at the Co/TiN interface: 20 mV.
  • Example 5 A cleaning composition was prepared in the same manner as in Example 1 so as to have the formulation shown in Table 1, and the obtained cleaning composition was subjected to cleaning performance evaluation and electrochemical evaluation.
  • electrochemical evaluation Co E CORR : -600 mV, Co I CORR : 4 ⁇ A/cm 2 , TiN E CORR : -640 mV, TiN I CORR : ND, and ⁇ E CORR at the Co/TiN interface: 40 mV.
  • Nonionic surfactants, aliphatic amines, nitrogen-containing heterocyclic compounds, and other additives are mixed with water so as to have the formulation shown in Table 1, and then the pH (25 ° C.) is 11.
  • a detergent composition was prepared by adding trimethyl-2-hydroxyethylammonium hydroxide (“choline”, 46% aqueous solution) so that Detergency performance evaluation and electrochemical evaluation were performed on the obtained detergent composition.
  • Nonionic surfactants, aliphatic amines, nitrogen-containing heterocyclic compounds, and other additives are mixed with water so as to have the formulation shown in Table 1, and then the pH (25 ° C.) is 11.
  • Ammonia (28% aqueous solution) was added to prepare a cleaning composition.
  • Detergency performance evaluation and electrochemical evaluation were performed on the obtained detergent composition.
  • Co E CORR ⁇ 500 mV
  • Co I CORR 2 ⁇ A/cm 2
  • ⁇ E CORR at the Co/Cu interface 60 mV.
  • Example 8 The N-vinyllactam polymer, aliphatic amines, nitrogen-containing heterocyclic compound, and other additives were mixed with water so as to obtain the formulation shown in Table 1, and then the pH (25°C) was adjusted. A detergent composition was prepared by adding potassium hydroxide so as to obtain 11. Detergency performance evaluation and electrochemical evaluation were performed on the obtained detergent composition. Electrochemical evaluation showed Co E CORR : ⁇ 440 mV, Co I CORR : ⁇ 1 ⁇ A/cm 2 , Cu E CORR : ⁇ 460 mV, Cu I CORR : 5 ⁇ A/cm 2 , and ⁇ E CORR at the Co/Cu interface: 20 mV. .
  • Example 9 The N-vinyllactam polymer, aliphatic amines, nitrogen-containing heterocyclic compound, and other additives were mixed with water so as to obtain the formulation shown in Table 1, and then the pH (25°C) was adjusted.
  • a detergent composition was prepared by adding trimethyl-2-hydroxyethylammonium hydroxide (“choline”, 46% aqueous solution) to 11. Detergency performance evaluation and electrochemical evaluation were performed on the obtained detergent composition.
  • Co E CORR ⁇ 490 mV
  • Co I CORR 10 ⁇ A/cm 2
  • Cu E CORR ⁇ 460 mV
  • Cu I CORR 5 ⁇ A/cm 2
  • ⁇ E CORR at the Co/Cu interface 30 mV.
  • Example 10 The N-vinyllactam polymer, aliphatic amines, nitrogen-containing heterocyclic compound, and other additives were mixed with water so as to obtain the formulation shown in Table 1, and then the pH (25°C) was adjusted. Ammonia (28% aqueous solution) was added to give a detergent composition of 11. Detergency performance evaluation and electrochemical evaluation were performed on the obtained detergent composition. Electrochemical evaluation showed Co E CORR : ⁇ 440 mV, Co I CORR : ⁇ 1 ⁇ A/cm 2 , Cu E CORR : ⁇ 460 mV, Cu I CORR : 5 ⁇ A/cm 2 , and ⁇ E CORR at the Co/Cu interface: 20 mV. .
  • Comparative example 1 A cleaning composition was prepared in the same manner as in Example 1 so as to have the formulation shown in Table 1, and the obtained cleaning composition was subjected to cleaning performance evaluation and electrochemical evaluation.
  • electrochemical evaluation Co E CORR : ⁇ 800 mV, Co I CORR : 306 ⁇ A/cm 2 , TiN E CORR : ⁇ 670 mV, TiN I CORR : 0.9 ⁇ A/cm 2 , and ⁇ E CORR at the Co/TiN interface: 130 mV. rice field.
  • Comparative example 2 A cleaning composition was prepared in the same manner as in Example 1 so as to have the formulation shown in Table 1, and the obtained cleaning composition was subjected to cleaning performance evaluation and electrochemical evaluation.
  • electrochemical evaluation Co E CORR : ⁇ 65 mV, Co I CORR : 54 ⁇ A/cm 2 , TiN E CORR : ⁇ 415 mV, TiN I CORR : 0.55 ⁇ A/cm 2 , and ⁇ E CORR at the Co/TiN interface: 320 mV. rice field.
  • Comparative example 3 A cleaning composition was prepared in the same manner as in Example 1 so as to have the formulation shown in Table 1, and the obtained cleaning composition was subjected to cleaning performance evaluation and electrochemical evaluation.
  • electrochemical evaluation Co E CORR : -700 mV, Co I CORR : 15 ⁇ A/cm 2 , TiN E CORR : -720 mV, TiN I CORR : ND, and ⁇ E CORR at the Co/TiN interface: 20 mV.
  • R 6 is H. Both R 7 and R 8 are linear alkyl groups having 1 to 12 carbon atoms, and the total number of carbon atoms of R 7 and R 8 is 11 to 13.
  • R 9 represents —C 2 H 4 —
  • Nonionic surfactant A-2 is N-(2-aminoethyl)-2-aminoethyl amine
  • R 11 and R 12 represent a methyl group
  • R 13 and R 14 represent an isobutyl group
  • R 19 represents -C ⁇ C-
  • Nonionic surfactant A-3 is N-(2-aminoethyl)-2-aminoethyl amine
  • R 20 represents —C 2 H 4 —
  • N-vinyllactam polymer A-4 polyvinylpyrrolidone (weight average molecular weight 7200)
  • N-vinyllactam polymer A-5 polyvinylpyrrolidone (weight average molecular weight 22000)
  • N-vinyl lactam polymer A-6 polyvinylpyrrolidone (weight average molecular weight 3000)
  • ⁇ Washing performance evaluation> (Preparation of Co-BTA particle dispersion) Prepare 1 L of a solution of 200 ⁇ mol/L cobalt (II) nitrate in a 0.01 mol/L pure nitric acid aqueous solution and 1 L of a solution of 200 ⁇ mol/L benzotriazole in a 0.01 mol/L nitric acid pure aqueous solution. Then, the two were mixed at room temperature to obtain 2 L of an aqueous solution in which insoluble aggregates of cobalt (II) ions and benzotriazole (hereinafter referred to as "Co-BTA particles”) were dispersed. Potassium hydroxide powder was added to the resulting aqueous solution to adjust the pH of the aqueous solution to 8.0 to obtain a Co-BTA particle dispersion.
  • a 1 cm square test piece was prepared by depositing Co, TiN, SiN, or SiO 2 to a thickness of about 5 to 200 nm, respectively, on a silicon wafer. 100 mL of the Co-BTA particle dispersion obtained above was placed in a beaker, and the test piece was immersed in the dispersion for 1 minute while stirring at 300 rpm using a magnetic rotor. After the immersion, the test piece taken out was rinsed with pure water and air-dried to remove moisture, thereby obtaining a substrate for cleaning evaluation.
  • the substrate for cleaning evaluation was immersed in 100 mL of the cleaning composition of the example or comparative example obtained above, and subjected to ultrasonic waves for 1 minute using an ultrasonic cleaner (8895, manufactured by Cole-Parmer).
  • a cleaning treatment was performed by irradiation (treatment conditions: output 115 W, 40 KHz, beaker internal temperature: 25°C).
  • the substrate for cleaning evaluation was taken out and rinsed with pure water, and the surface state of the substrate for cleaning evaluation was observed in the same manner as described above.
  • FIG. 1 shows an AFM observation image of the obtained substrate surface for cleaning evaluation.
  • a 1 cm square test piece was prepared by depositing Co, Cu, TiN, SiN, or SiO 2 with a thickness of about 5 to 1500 nm on a silicon wafer.
  • a detergent composition that does not corrode must simultaneously satisfy a corrosion current value of 10 ⁇ A/cm 2 or less and a corrosion potential difference of 60 mV or less at the interface of dissimilar metals.
  • this evaluation criterion was satisfied at the same time, and it can be judged that the occurrence of corrosion can be suppressed extremely well.
  • the detergent compositions of Comparative Examples 1 to 3 were used, at least one of the evaluation criteria was not satisfied.
  • Nonionic surfactant A The same compound as the nonionic surfactant A-1 used in Example 1 above.
  • Nonionic surfactant B The same compound as the nonionic surfactant A-1 used in Example 1 above.
  • Nonionic surfactant B The same compound as the nonionic surfactant A-1 used in Example 1 above.
  • N-vinyllactam polymer polyvinylpyrrolidone (weight average molecular weight 7200)
  • EDTA ethylenediaminetetraacetic acid
  • Preparation Example 5 Preparation of SiO 2 substrate for cleaning performance evaluation
  • a 1 cm square test piece was prepared by depositing SiO 2 to a thickness of about 10 to 50 nm on a silicon wafer, and 100 mL of the positively charged ceria nanoparticle dispersion was prepared.
  • A-1 or A-2 was placed in a beaker, and the test piece was immersed for 1 minute while stirring at 300 rpm with a magnetic rotor. The removed test pieces were rinsed with pure water and dried at room temperature to obtain cleaning performance evaluation substrates A-1 and A-2.
  • the surface state of the substrate was observed using an atomic force microscope (AFM).
  • the equipment used was XE-300P (manufactured by Park Systems), and a PPP-NCHR AFM probe was used in non-contact mode (observation conditions: scan rate 0.5 Hz, observation area 5 ⁇ m ⁇ 5 ⁇ m).
  • Preparation Example 6 Preparation of SiN substrate for cleaning performance evaluation
  • a 1 cm square test piece was prepared by depositing SiN to a thickness of about 10 to 50 nm on a silicon wafer, and 100 mL of the negatively charged ceria nanoparticle dispersion B- was prepared. 1 or B-2 was placed in a beaker and the test piece was immersed for 1 minute while stirring at 300 rpm with a magnetic rotor. The removed test pieces were rinsed with pure water and dried at room temperature to obtain cleaning performance evaluation substrates B-1 and B-2. The surface state of the substrate was observed using an atomic force microscope (AFM). The equipment used was XE-300P (manufactured by Park Systems), and a PPP-NCHR AFM probe was used in non-contact mode (observation conditions: scan rate 0.5 Hz, observation area 5 ⁇ m ⁇ 5 ⁇ m).
  • washing treatment 100 mL of the cleaning composition of the above example or comparative example was weighed into a beaker, the cleaning performance evaluation board was immersed in the cleaning composition, and an ultrasonic cleaner (8895, manufactured by Cole-Parmer) was used. Then, cleaning treatment was performed by ultrasonic irradiation for 1 minute (treatment conditions: output 115 W, 40 kHz, temperature in beaker: 25°C). After the ultrasonic wave irradiation, the cleaning performance evaluation substrate taken out was rinsed with pure water, and the surface state of the cleaning performance evaluation substrate was observed in the same manner as described above.
  • FIG. 2 shows cleaning treatment of SiO 2 substrates for cleaning performance evaluation (evaluation substrates A-1 and A-2) using the cleaning compositions of Examples 11-12, 17-18 and Comparative Examples 4-5.
  • 2 shows AFM images showing the surface condition of the substrate with and without cleaning. These cleaning compositions do not contain hydrogen peroxide. From the surface state of the unwashed cleaning performance evaluation substrate, when contaminated with 90 nm colloidal ceria (ceria nanoparticle dispersion liquid A-1), white foreign matter was confirmed, and 30 nm colloidal ceria (ceria nanoparticle dispersion liquid A It can be seen that in the case of contamination in -2), the size of the foreign matter is reduced and the density is increased.
  • FIG. 3 shows the results of cleaning the cleaning performance evaluation SiO 2 substrates (evaluation substrates A-1 and A-2) using the cleaning compositions of Examples 13 to 15 and Comparative Example 6.
  • 2 shows an AFM image representing the surface state.
  • These cleaning compositions contain hydrogen peroxide.
  • the cleaning compositions of Examples 13 to 15 were used, good cleaning performance was confirmed, and even when the colloidal ceria had a fine particle size of 30 nm, it was possible to cleanly remove the particles, demonstrating excellent cleaning performance. confirmed.
  • the cleaning composition of Comparative Example 6 containing the nonionic surfactant B was used, cleaning residues were observed even when the colloidal ceria had a particle size of 90 nm.
  • FIG. 4 shows the case where the cleaning performance evaluation SiN substrates (evaluation substrates B-1 and B-2) were cleaned using the cleaning compositions of Examples 11, 13, and 16, and when they were not cleaned. 4 shows an AFM image showing the surface condition of the substrate.
  • the cleaning compositions of Examples exhibited excellent cleaning performance when compared with uncleaned substrates, both when the particle size of colloidal ceria was 90 nm and when the particle size of colloidal ceria was 30 nm. It was confirmed to have
  • component (2A) a nonionic surfactant or N-vinyllactam polymer having an alkylene oxide adduct structure of an aliphatic alcohol
  • component (2B) an organic acid compound
  • (2C) a pH adjuster.
  • the high cleaning performance of the cleaning composition for cleaning was shown. Cleaner compositions containing an oxidizing agent such as hydrogen peroxide also showed excellent cleaning performance, but the performance levels were comparable to those without. It was determined that the use of oxidizing agents was not necessary due to concerns about corrosion of metal parts and health hazards to the human body.
  • Examples 19-21 After mixing a nonionic surfactant, an organic acid compound, and ammonium carbamate with water so that the mass % of each component in 100 mass % of the cleaning composition as shown in Table 4, the pH is 12 (25 ° C.), tetramethylammonium hydroxide (25% aqueous solution), trimethyl-2-hydroxyethylammonium hydroxide (“choline”, 50% aqueous solution), or dimethylbis(2-hydroxyethyl)ammonium hydroxide (50% aqueous solution) was added to prepare a detergent composition.
  • tetramethylammonium hydroxide (25% aqueous solution)
  • trimethyl-2-hydroxyethylammonium hydroxide (“choline”, 50% aqueous solution)
  • dimethylbis(2-hydroxyethyl)ammonium hydroxide 50% aqueous solution
  • Examples 22-23 After mixing the nonionic surfactant and the organic acid compound with water so that the mass % of each component in 100 mass % of the cleaning composition as shown in Table 4, the pH becomes 12 (25 ° C.).
  • a detergent composition was prepared by adding dimethylbis(2-hydroxyethyl)ammonium hydroxide (50% aqueous solution) as follows.
  • Comparative example 7 Hydrogen peroxide (30% aqueous solution) and ammonia (29% aqueous solution) were mixed with water so that the mass % of each component in 100% by mass of the cleaning composition as shown in Table 4 was mixed to obtain a cleaning composition. prepared the product.
  • the obtained cleaning composition and the cleaning composition of Example 11 were evaluated for etching rate by the following method.
  • Table 4 shows the results. ⁇ Evaluation of etching grade> 5 mL of each cleaning composition was placed in a bottle, and a 1.5 cm 2 silicon oxide (SiO 2 ) film-coated wafer was immersed therein and left at room temperature for 6 days. Thereafter, the treated body was taken out from the cleaning agent composition, washed with water, and then the cross section was observed with an SEM to measure the film thickness of the silicon oxide film. The etching rate was calculated from the silicon oxide film thickness before and after the treatment.
  • component (2A) a nonionic surfactant and / or N-vinyl lactam polymer having an alkylene oxide adduct structure of an aliphatic alcohol
  • (2C) a pH adjuster It was confirmed that the cleaning composition containing and is excellent in the etching rate for silicon oxide films.

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Abstract

Le but de la présente invention est de fournir une composition d'agent de nettoyage qui est destinée à une étape post-CMP et qui présente une excellente performance d'élimination et une inhibition de fixation pour des résidus métalliques ou des résidus organiques restant sur une surface polie obtenue par aplatissement d'un substrat, et qui a une excellente inhibition de la corrosion. La présente invention concerne : une composition d'agent de nettoyage pour une étape post-CMP dans un procédé de production de semi-conducteur, la composition comprenant (1A) au moins un composé choisi dans le groupe constitué par les polymères à base de N-vinyllactame et les tensioactifs non ioniques comprenant un adduit d'oxyde d'alkylène d'un alcool ayant 6 atomes de carbone ou plus, (1B) une amine aliphatique, et (1C) au moins un inhibiteur de corrosion choisi dans le groupe constitué par des composés hétérocycliques contenant de l'azote et des composés carboxylate ; et une composition d'agent de nettoyage pour une étape post-CMP, la composition comprenant (2A) au moins un composé choisi dans le groupe constitué par les polymères à base de N-vinyllactame et les tensioactifs non ioniques ayant une structure d'adduit d'oxyde d'alkylène d'un alcool aliphatique, (2B) un composé acide organique, et (2C) un conditionneur de pH.
PCT/JP2022/026835 2021-07-08 2022-07-06 Composition d'agent de nettoyage pour une étape post-cmp WO2023282287A1 (fr)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
JP2016526070A (ja) * 2013-05-17 2016-09-01 アドバンスド テクノロジー マテリアルズ，インコーポレイテッド 表面からセリア粒子を除去するための組成物及び方法
JP2017120844A (ja) * 2015-12-28 2017-07-06 花王株式会社 半導体デバイス用基板用の酸性洗浄剤組成物
JP2018503723A (ja) * 2015-01-05 2018-02-08 インテグリス・インコーポレーテッド 化学機械研磨後製剤および使用方法
WO2019073931A1 (fr) * 2017-10-10 2019-04-18 三菱ケミカル株式会社 Fluides de nettoyage, procédé de nettoyage et procédé de production de tranche de semi-conducteur
WO2019171790A1 (fr) * 2018-03-08 2019-09-12 株式会社フジミインコーポレーテッド Composition de traitement de surface, procédé de production de composition de traitement de surface, procédé de traitement de surface et procédé de production de substrat semi-conducteur
JP2020504460A (ja) * 2017-01-18 2020-02-06 インテグリス・インコーポレーテッド セリア粒子を表面から除去するための組成物及び方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016526070A (ja) * 2013-05-17 2016-09-01 アドバンスド テクノロジー マテリアルズ，インコーポレイテッド 表面からセリア粒子を除去するための組成物及び方法
JP2018503723A (ja) * 2015-01-05 2018-02-08 インテグリス・インコーポレーテッド 化学機械研磨後製剤および使用方法
JP2017120844A (ja) * 2015-12-28 2017-07-06 花王株式会社 半導体デバイス用基板用の酸性洗浄剤組成物
JP2020504460A (ja) * 2017-01-18 2020-02-06 インテグリス・インコーポレーテッド セリア粒子を表面から除去するための組成物及び方法
WO2019073931A1 (fr) * 2017-10-10 2019-04-18 三菱ケミカル株式会社 Fluides de nettoyage, procédé de nettoyage et procédé de production de tranche de semi-conducteur
WO2019171790A1 (fr) * 2018-03-08 2019-09-12 株式会社フジミインコーポレーテッド Composition de traitement de surface, procédé de production de composition de traitement de surface, procédé de traitement de surface et procédé de production de substrat semi-conducteur

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