WO2022264869A1 - 洗浄組成物、半導体基板の洗浄方法、および、半導体素子の製造方法 - Google Patents
洗浄組成物、半導体基板の洗浄方法、および、半導体素子の製造方法 Download PDFInfo
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- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3409—Alkyl -, alkenyl -, cycloalkyl - or terpene sulfates or sulfonates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive 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
- H01L21/02—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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Definitions
- the present invention relates to cleaning compositions.
- Patent Document 1 discloses a cleaning solution containing organic polymer particles having a crosslinked structure and a surfactant.
- Patent Document 1 The present inventors found that when the cleaning solution (cleaning composition) disclosed in Patent Document 1 was used for cleaning semiconductor substrates, it was difficult to achieve both residue removability and copper corrosion resistance. did.
- an object of the present invention is to provide a cleaning composition that is excellent in removability of residues (especially residues after CMP) and excellent in anticorrosion of copper.
- Another object of the present invention is to provide a method for cleaning a semiconductor substrate and a method for manufacturing a semiconductor element.
- citric acid 1-hydroxyethane-1,1-diphosphonic acid
- a sulfonic acid-based surfactant including water and The mass ratio of the citric acid content to the 1-hydroxyethane-1,1-diphosphonic acid content is 20 to 150, The mass ratio of the content of citric acid to the content of the sulfonic acid surfactant is 70 to 1500, A cleaning composition having a pH of 0.10 to 4.00.
- the sulfonic acid-based surfactant is an alkylbenzenesulfonic acid-based surfactant 1 containing an alkyl group having 10 carbon atoms; an alkylbenzenesulfonic acid-based surfactant 2 containing an alkyl group having 11 carbon atoms; an alkylbenzenesulfonic acid-based surfactant 3 containing an alkyl group having 12 carbon atoms;
- the cleaning composition according to any one of [1] to [4], comprising an alkylbenzenesulfonic acid surfactant 4 containing an alkyl group having 13 carbon atoms.
- the cleaning composition which is excellent in the removability of a residue (especially the residue after CMP), and is excellent in copper corrosion resistance can be provided. Further, according to the present invention, it is possible to provide a method for cleaning a semiconductor substrate and a method for manufacturing a semiconductor element.
- a numerical range represented by “to” means a range including the numerical values before and after “to” as lower and upper limits.
- ppm is an abbreviation for "parts per million” and means 10 ⁇ 6 .
- ppb in the present specification is an abbreviation of "parts per billion” and means 10 -9 .
- the compounds described herein may include isomers (compounds having the same number of atoms but different structures), optical isomers and isotopes unless otherwise specified.
- one kind of isomer and isotope may be contained, or plural kinds thereof may be contained.
- the “content" of the component means the total content of the two or more kinds of components.
- the cleaning composition of the present invention contains citric acid, 1-hydroxyethane-1,1-diphosphonic acid (hereinafter also referred to as "HEDPO"), a sulfonic acid surfactant, and water, and HEDPO
- the mass ratio of the citric acid content to the content of is 20 to 150
- the mass ratio of the citric acid content to the sulfonic acid surfactant content is 70 to 1500
- the pH is 0.10 to 4.00.
- the cleaning composition contains citric acid and HEDPO in a specific range of mass ratio, it exhibits an appropriate dissolving ability, and furthermore, the cleaning composition contains a sulfonic acid-based surfactant. It is presumed that the removability of the residue is improved by including citric acid in a specific range of mass ratio. As a result, the cleaning composition of the present invention is presumed to have excellent residue removability and copper corrosion resistance. Components contained in the cleaning composition, properties of the cleaning composition, and preparation of the cleaning composition are described in detail below.
- the cleaning composition of the present invention comprises citric acid, 1-hydroxyethane-1,1-diphosphonic acid (HEDPO), a sulfonic acid surfactant, and water.
- the cleaning composition of the present invention may contain other components described later. Each component contained in the cleaning composition and the content ratio by mass of the component will be described in detail below.
- the citric acid preferably has a low impurity content, for example semiconductor grade.
- the content of citric acid relative to the total mass of the cleaning composition is preferably 0.1 to 35.0% by mass, more preferably 1.0 to 35.0% by mass, in terms of better residue removability and copper corrosion resistance. More preferably, 20.0 to 35.0% by mass is even more preferable.
- the 1-hydroxyethane-1,1-diphosphonic acid (HEDPO) preferably has a low impurity content, eg semiconductor grade.
- the content of HEDPO with respect to the total weight of the cleaning composition is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass. 0.4 to 0.8% by weight is particularly preferred.
- the mass ratio of the citric acid content to the HEDPO content is 20-150.
- the mass ratio is preferably from 30 to 100, more preferably from 40 to 80, and even more preferably from 50 to 60, from the viewpoint of better residue removability and copper corrosion resistance.
- a sulfonic acid-based surfactant is a surfactant containing a sulfo group as a hydrophilic group out of the hydrophobic group and hydrophilic group possessed by the surfactant molecule.
- the hydrophobic group in the sulfonic acid surfactant is not particularly limited, and examples thereof include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof.
- the number of carbon atoms in the hydrophobic group is preferably 6 or more, more preferably 10 or more.
- the upper limit of the number of carbon atoms in the hydrophobic group is not particularly limited, it is preferably 24 or less, more preferably 20 or less.
- sulfonic acid-based surfactants examples include alkylarylsulfonic acid-based surfactants (e.g., alkylbenzenesulfonic acid-based surfactants, alkylnaphthalenesulfonic acid-based surfactants), alkyldiphenyl ether disulfonic acid-based surfactants, and polyoxyethylene alkylsulfate-based surfactants, with alkylarylsulfonic acid-based surfactants being preferred. That is, a sulfonic acid-based surfactant having an alkyl group and a sulfo group in the surfactant molecule and containing an aromatic hydrocarbon ring in the molecule is preferred.
- alkylarylsulfonic acid-based surfactants e.g., alkylbenzenesulfonic acid-based surfactants, alkylnaphthalenesulfonic acid-based surfactants
- the alkyl group of the alkylarylsulfonic acid-based surfactant may be linear or branched, preferably branched.
- the number of carbon atoms in the alkyl group is preferably 8 or more, more preferably 8-20, even more preferably 10-13.
- aromatic hydrocarbon rings contained in alkylarylsulfonic acid-based surfactants include benzene rings and naphthalene rings.
- the sulfo group of the alkylarylsulfonic acid-based surfactant is preferably directly bonded to the aromatic hydrocarbon ring.
- a sulfo group may form a salt with a cation.
- a surfactant represented by formula (A) is preferred.
- R a represents an alkyl group having 8 or more carbon atoms.
- Ar a represents an arylene group.
- the preferred range of the number of carbon atoms in the alkyl group is as described above.
- the arylene group may be either monocyclic or polycyclic.
- the arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms.
- a phenylene group or a naphthylene group is preferred.
- the sulfonic acid-based surfactant include alkylbenzenesulfonic acid-based surfactants. That is, a sulfonic acid-based surfactant in which the surfactant molecule has an alkyl group and a sulfo group and the surfactant molecule contains a benzene ring in the molecule is preferred.
- the alkylbenzenesulfonic acid-based surfactant is also referred to as "ABS”.
- the alkyl group of ABS may be linear or branched, preferably branched.
- the number of carbon atoms in the alkyl group of ABS is preferably 8 or more, more preferably 8-20, even more preferably 10-13.
- ABS includes an embodiment in which Ara in formula (A) is a phenylene group.
- ABS examples include octylbenzenesulfonic acid, nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, hexadecanebenzenesulfonic acid, heptadecanebenzenesulfonic acid, octadecanebenzenesulfonic acid, nonadecanbenzenesulfonic acid, eicosylbenzenesulfonic acid, decyldiphenyloxide disulfonic acid, undecyldiphenyloxide disulfonic acid, dodecyldiphenyloxide disulfonic acid, and tri Decyldiphenyl oxide disulfonic acid and
- the sulfonic acid-based surfactant is an alkylbenzenesulfonic acid-based surfactant 1 (hereinafter also referred to as "ABS1") containing an alkyl group having 10 carbon atoms, and an alkylbenzenesulfonic acid-based interface containing an alkyl group having 11 carbon atoms.
- ABS1 alkylbenzenesulfonic acid-based surfactant 1
- ABS1 includes an aspect in which Ara in formula (A) is a phenylene group and R a is an alkyl group having 10 carbon atoms.
- ABS2 includes an embodiment in which A a in formula (A) is a phenylene group and R a is an alkyl group having 11 carbon atoms.
- ABS3 includes an aspect in which Ara in formula (A) is a phenylene group and R a is an alkyl group having 12 carbon atoms.
- ABS4 includes an embodiment in which A a in formula (A) is a phenylene group and R a is an alkyl group having 13 carbon atoms.
- the content of ABS1 relative to the total mass of ABS1-4 is not particularly limited, but is preferably 5-50% by mass.
- the content of ABS2 with respect to the total mass of ABS1-4 is not particularly limited, but is preferably 20-50% by mass.
- the content of ABS3 with respect to the total mass of ABS1-4 is not particularly limited, but is preferably 20-50% by mass.
- the content of ABS4 with respect to the total mass of ABS1-4 is not particularly limited, but is preferably 20-50% by mass.
- the content of the sulfonic acid surfactant relative to the total weight of the cleaning composition is preferably 0.0001 to 1.0% by mass, more preferably 0.001 to 0.8% by mass, and 0.02 to 0.2% by mass. % is more preferred, and 0.05 to 0.1% by mass is particularly preferred.
- the mass ratio of the content of citric acid to the content of the sulfonic acid surfactant is 70-1500.
- the mass ratio is preferably from 200 to 600, more preferably from 300 to 500, and even more preferably from 410 to 440, from the viewpoint of superior residue removability and copper corrosion resistance.
- the mass ratio of the HEDPO content to the sulfonic acid surfactant content is preferably 0.5-30, more preferably 1-20, and even more preferably 5-10.
- water As water, distilled water, ion-exchanged water, and purified water such as ultrapure water are preferable, and ultrapure water used in semiconductor manufacturing is more preferable.
- the water content relative to the total mass of the cleaning composition is preferably 50.00 to 99.99% by mass, more preferably 60.00 to 98.00% by mass, even more preferably 65.00 to 85.00% by mass, 68.00 to 75.00% by weight is particularly preferred.
- ingredients that the cleaning composition may contain include, for example, metal ions, phosphate ions, inorganic particles, organic particles, amine compounds, anticorrosives, and pH adjusters.
- surfactants other than sulfonic acid-based surfactants may be included.
- the cleaning composition may contain metal ions.
- the metal elements of the metal ions include Fe, Co, Na, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn, and Ag.
- the content of copper ions with respect to the total mass of the cleaning composition is preferably 0.5 mass ppb or less. Although the lower limit is not particularly limited, it is preferably not detected.
- the content of metal ions can be determined by a known method such as ICP-MS (Inductively Coupled Plasma-Mass Spectrometry). In this specification, the content of metal ions is measured by ICP-MS.
- the cleaning composition may contain phosphate ions.
- Phosphate ions may be included as impurities in each of the above components.
- the content of phosphate ions relative to the total mass of the cleaning composition is preferably 1.0% by mass or less, more preferably 0.1% by mass or less, and 0.01% by mass or less. is more preferred.
- Phosphate ions are preferably not detected in the cleaning composition, but the content of phosphate ions is often 0.001% by mass or more relative to the total mass of the cleaning composition.
- Phosphate ions can be determined by known methods, such as ion chromatography and colorimetric methods using ammonium molybdate. Methods for adjusting the content of phosphate ions include, for example, a method of purifying the components contained in the cleaning composition and the cleaning composition after adjustment using distillation, an ion exchange resin, or the like.
- the cleaning composition may contain at least one of inorganic particles and organic particles.
- the total content of the inorganic particles and the organic particles is preferably 1.0% by mass or less, more preferably 0.1% by mass or less, relative to the total mass of the cleaning composition.
- 0.01% by mass or less is more preferable.
- the lower limit is not particularly limited, it may be 0.1 mass ppb or more.
- the inorganic and organic particles contained in the cleaning composition include particles such as organic and inorganic solids contained as impurities in raw materials and organic and inorganic solids introduced as contaminants during preparation of the cleaning composition. Particles such as substances that do not ultimately dissolve in the cleaning composition but exist as particles fall under this category.
- the content of inorganic particles and organic particles present in the cleaning composition can be measured in a liquid phase using a commercially available measurement device in a light scattering type particle measurement system in liquid using a laser as a light source.
- Methods for removing inorganic particles and organic particles include, for example, purification treatment such as filtering, which will be described later.
- the cleaning composition may contain an amine compound.
- An amine compound is a compound having an amino group.
- the amino group of the amine compound is selected from the group consisting of a primary amino group ( -NH2 ), a secondary amino group (>NH) and a tertiary amino group (>N-). at least one amino group; When the amine compound has multiple series of amino groups, it is classified into the amine compound having the highest amino group among them.
- an amine compound having a primary amino group and a secondary amine group is an amine compound having a secondary amine group.
- Amine compounds include, for example, aliphatic amines and aminoalcohols (aliphatic amines having a hydroxy group).
- the amine compound may be either linear (linear or branched) or cyclic. You may use an amine compound individually by 1 type or in 2 or more types.
- the cleaning composition may contain anticorrosion agents.
- the anticorrosive agent includes, for example, a compound having a heteroatom, preferably a compound having a heterocyclic ring (heterocyclic compound), and more preferably a compound having a polycyclic heterocyclic ring.
- a purine compound, an azole compound or a reducing sulfur compound is preferred.
- the anti-corrosion agent is preferably a different compound than those listed above that may be included in the cleaning composition. You may use an anticorrosive by 1 type individual or 2 or more types.
- the content of the anticorrosive agent with respect to the total mass of the cleaning composition is preferably 0.01 to 10.0% by mass, more preferably 1.0 to 10.0% by mass. 0 to 8.0% by mass is more preferable.
- the cleaning composition may contain a surfactant different from the sulfonic acid-based surfactant (hereinafter also referred to as "another surfactant”).
- Other surfactants are compounds having a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule, such as nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. Surfactants are included. When the cleaning composition contains other surfactants, the anti-corrosion performance of the metal film and the removability of abrasive fine particles are more excellent.
- surfactants for example, paragraphs [0092] to [0096] of JP-A-2015-158662, paragraphs [0045] to [0046] of JP-A-2012-151273 and JP-A-2009-147389 Also included are compounds described in paragraphs [0014] to [0020] of the publication, the contents of which are incorporated herein.
- Other surfactants may be used singly or in combination of two or more.
- the content of the other surfactant with respect to the total mass of the cleaning composition is preferably 0.001 to 8.0% by mass, and 0.005 to 5.0% by mass. is more preferable, and 0.01 to 3.0% by mass is even more preferable.
- the cleaning composition may contain pH adjusting agents to adjust and maintain the pH of the cleaning composition.
- the cleaning composition may be adjusted to the pH range described below with a pH adjuster.
- a pH adjuster is a basic or acidic compound, different from the compounds described above that may be included in the cleaning composition.
- pH adjusters include quaternary ammonium compounds, basic compounds, and acidic compounds, with quaternary ammonium compounds, sulfuric acid, or potassium hydroxide being preferred.
- the pH of the cleaning composition may be adjusted by adjusting the amount of each component added. Examples of pH adjusters include paragraphs [0053] and [0054] of WO2019-151141 and paragraph [0021] of WO2019-151001, the contents of which are herein incorporated into.
- the cleaning composition contains a pH adjuster
- the content of the pH adjuster with respect to the total weight of the cleaning composition can be selected according to the types and amounts of other components, and is preferably 0.01 to 10.0% by mass, and 0 0.05 to 5.0 mass % is more preferred, and 0.05 to 3.0 mass % is even more preferred.
- the pH of the cleaning composition of the present invention is from 0.10 to 4.00.
- the pH of the cleaning composition is preferably from 0.50 to 3.00, more preferably from 1.00 to 2.00, and even more preferably from 1.00 to 1.50, from the viewpoint of better anticorrosiveness of copper.
- the pH of the cleaning composition is obtained by measuring at 25° C. using a pH meter (F-51 (trade name) manufactured by Horiba, Ltd.).
- Methods for adjusting the pH include, for example, a method of adjusting the type and content of each component that can be contained in the cleaning composition, and a method of adding the pH adjuster described above.
- the electrical conductivity of the cleaning composition is preferably 0.05-11.0 mS/cm.
- the electrical conductivity of the cleaning composition is more preferably 1.00 to 11.0 mS/cm, even more preferably 4.00 to 11.0 mS/cm.
- the electrical conductivity of the cleaning composition is obtained by measuring at 25° C. using an electrical conductivity meter (portable type D-70/ES-70 series, manufactured by Horiba, Ltd.). Examples of the method for adjusting the electrical conductivity include a method for adjusting the type and content of each component that can be contained in the cleaning composition.
- the method for preparing the cleaning composition is not particularly limited, and for example, the cleaning composition can be produced by mixing the components described above.
- the order and/or timing of mixing the components described above is not particularly limited.
- a method of mixing citric acid, HEDPO, a sulfonic acid-based surfactant, and other components with water, and water, HEDPO, a sulfonic acid-based surfactant, and, with respect to an aqueous citric acid solution A method of mixing other components may be mentioned.
- each component may be mixed all at once, or may be divided and mixed a plurality of times.
- each component to be mixed may be a solid or an aqueous solution.
- the stirring device and stirring method used for mixing the cleaning composition are not particularly limited, and known devices and methods may be used.
- Stirrers include, for example, industrial mixers, portable stirrers, mechanical stirrers, and magnetic stirrers.
- the mixing of each component in the preparation of the cleaning composition, the purification treatment described below, and the storage temperature of the manufactured cleaning composition are preferably 40°C or lower, more preferably 30°C or lower.
- the lower limit of the storage temperature is not particularly limited, it is preferably 5°C or higher, more preferably 10°C or higher.
- any one or more of the raw materials for producing the cleaning composition are preferably subjected to purification treatment in advance. Further, a purification treatment may be performed on the cleaning composition produced by the above method.
- the purification treatment is not particularly limited, and examples thereof include known methods such as distillation, ion exchange, and filtration.
- the degree of purification is not particularly limited, but for example, it is preferable to purify until the purity of the raw material reaches 99% by mass or more, and it is more preferable to purify until the purity of the stock solution reaches 99.9% by mass or more.
- Specific purification methods include, for example, a method of passing the raw material through an ion exchange resin or an RO membrane (Reverse Osmosis Membrane), distillation of the raw material, and filtering, which will be described later.
- a purification treatment a plurality of the purification methods described above may be combined and implemented.
- secondary purification is carried out by passing it through a purification device consisting of a cation exchange resin, an anion exchange resin, or a mixed bed ion exchange resin. You may Further, the refining process may be performed multiple times.
- the filter used for filtering is not particularly limited as long as it has been conventionally used for filtering purposes.
- polytetrafluoroethylene (PTFE) and fluorine-based resins such as tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide-based resins such as nylon, and polyethylene and polypropylene (PP)
- Filters made of polyolefin resins are included.
- materials selected from the group consisting of polyethylene, polypropylene (including high-density polypropylene), fluorine-based resins (including PTFE and PFA), and polyamide-based resins (including nylon) are preferred.
- a fluororesin filter is more preferable.
- the critical surface tension of the filter is preferably 70-95 mN/m, more preferably 75-85 mN/m.
- the value of the critical surface tension of the filter is the manufacturer's nominal value.
- the pore size of the filter is preferably 2-20 nm, more preferably 2-15 nm.
- Filtering may be performed only once, or may be performed twice or more. If filtering is performed more than once, the filters used may be the same or different.
- the temperature for filtering is preferably room temperature (25°C) or lower, more preferably 23°C or lower, and even more preferably 20°C or lower.
- the lower limit of the temperature is preferably 0°C or higher, more preferably 5°C or higher, and even more preferably 10°C or higher.
- the cleaning composition (including the embodiment of the diluted cleaning composition described below) can be stored, transported, and used by filling it in any container as long as corrosiveness and the like are not a problem.
- a container for use in semiconductors that has a high degree of cleanliness inside and that suppresses the elution of impurities into the cleaning composition from the inner wall of the storage portion of the container.
- Examples of such containers include various containers commercially available as containers for semiconductor cleaning compositions. Examples of commercially available machines include, but are not limited to, the "Clean Bottle” series manufactured by Aicello Chemical Co., Ltd. and the “Pure Bottle” manufactured by Kodama Resin Industry.
- the liquid-contacting part of the container, such as the inner wall of the containing part, with the cleaning composition is made of a fluorine-based resin (perfluoro resin), or is subjected to antirust treatment and/or , preferably made of metal subjected to metal elution prevention treatment.
- the inner wall of the container is preferably made of resin or metal treated to prevent rust and prevent metal elution.
- resins include one or more resins selected from the group consisting of polyethylene resins, polypropylene resins, and polyethylene-polypropylene resins, and resins different from these resins described below.
- metals to which rust prevention and metal elution prevention treatments are applied include stainless steel, Hastelloy, Inconel, and Monel.
- a fluororesin perfluoro resin
- a container whose inner wall is made of fluororesin it is possible to suppress the problem of elution of oligomers of ethylene or propylene compared to a container whose inner wall is made of polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin.
- a specific example of such a container having an inner wall made of a fluororesin is a FluoroPure PFA composite drum manufactured by Entegris.
- the container described can also be used.
- quartz and electropolished metal material are preferably used in addition to the above-mentioned fluororesin.
- the metal material used for producing the electropolished metal material contains at least one selected from the group consisting of chromium and nickel, and the total content of chromium and nickel is the total mass of the metal material. It is preferably a metal material having a content of more than 25% by mass, and examples thereof include stainless steel and nickel-chromium alloys.
- the total content of chromium and nickel in the metal material is more preferably 30% by mass or more with respect to the total mass of the metal material.
- the upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is preferably 90% by mass or less.
- the method for electropolishing a metal material is not particularly limited, and a known method can be used.
- a known method can be used.
- the methods described in paragraphs [0011] to [0014] of JP-A-2015-227501 and paragraphs [0036] to [0042] of JP-A-2008-264929 can be used.
- the interior of these containers is preferably cleaned before being filled with the cleaning composition. It is preferable that the liquid used for cleaning has a reduced amount of metal impurities in the liquid.
- the cleaning composition may be bottled in a container such as a gallon bottle or a coated bottle, and transported and stored.
- the inside of the container may be replaced with an inert gas (nitrogen, argon, etc.) with a purity of 99.99995% by volume or more.
- a gas with a low water content is particularly preferred.
- normal temperature may be used, but the temperature may be controlled within the range of -20 to 20°C in order to prevent deterioration.
- the proportion of the volume other than the cleaning composition in the container is preferably 1 to 30% by volume, more preferably 3 to 20% by volume, and even more preferably 5 to 15% by volume.
- the cleanroom preferably meets 14644-1 cleanroom standards.
- ISO International Organization for Standardization
- ISO Class 1 ISO Class 2, ISO Class 3, and ISO Class 4 are preferred, ISO Class 1 or ISO Class 2 is more preferred, and ISO Class 1 is preferred. is more preferred.
- the cleaning composition is preferably used in the step of cleaning semiconductor substrates in the manufacturing process of semiconductor substrates.
- the cleaning composition is preferably used in a cleaning process for cleaning a semiconductor substrate that has undergone chemical mechanical polishing (CMP) processing.
- CMP chemical mechanical polishing
- the cleaning composition can be used in a buffing process, as described below.
- the cleaning composition can also be used for cleaning equipment used in the manufacturing process of semiconductor substrates.
- a diluted cleaning composition obtained by diluting the cleaning composition may be used for cleaning the semiconductor substrate. Objects to be cleaned for which the cleaning composition is preferably used are described in detail below.
- Objects to be cleaned with the cleaning composition include, for example, semiconductor substrates (more specifically, semiconductor substrates having metal inclusions).
- the object to be cleaned is preferably a semiconductor substrate having a metal-containing substance after the CMP process, which will be described later, and a semiconductor substrate having a metal-containing substance subjected to buffing after the CMP process.
- Metals contained in metal inclusions include, for example, copper (Cu), cobalt (Co), tungsten (W), molybdenum (Mo), ruthenium (Ru), aluminum (Al), titanium (Ti), and tantalum (Ta). , chromium (Cr), hafnium (Hf), osmium (Os), platinum (Pt), nickel (Ni), manganese (Mn), zirconium (Zr), palladium (Pd), lanthanum (La), and iridium ( Ir) at least one metal M selected from the group consisting of
- the metal-containing material may be any substance containing a metal (metal atom). things are mentioned.
- the metal inclusions may be mixtures containing two or more of these compounds.
- the oxides, nitrides, and oxynitrides may be any of composite oxides, composite nitrides, and composite oxynitrides containing metals.
- the content of metal atoms in the metal-containing material is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, relative to the total mass of the metal-containing material.
- the upper limit is preferably 100% by mass or less because the metal inclusion may be the metal itself.
- the semiconductor substrate preferably has metal inclusions containing metal M, and metal inclusions containing at least one metal selected from the group consisting of Cu, Co, W, Mo, Ru, Al, Ti, and Ta. and more preferably has a metal inclusion containing at least one metal selected from the group consisting of Cu, Co, W, Mo, and Ru, and has a metal inclusion containing Cu is particularly preferred.
- Examples of semiconductor substrates that are objects to be cleaned with the cleaning composition include substrates having a metal wiring film, a barrier metal, and an insulating film on the surface of a wafer that constitutes the semiconductor substrate.
- wafers that make up the semiconductor substrate include silicon (Si) wafers, silicon carbide (SiC) wafers, wafers made of silicon-based materials such as resin-based wafers containing silicon (glass epoxy wafers), gallium phosphide ( GaP) wafers, gallium arsenide (GaAs) wafers, and indium phosphide (InP) wafers.
- Silicon wafers include n-type silicon wafers obtained by doping silicon wafers with pentavalent atoms (e.g., phosphorus (P), arsenic (As), and antimony (Sb)), and silicon wafers with trivalent atoms.
- It may be a p-type silicon wafer doped with (eg, boron (B), gallium (Ga), etc.).
- the silicon of the silicon wafer may be, for example, amorphous silicon, monocrystalline silicon, polycrystalline silicon, or polysilicon.
- the semiconductor substrate may have an insulating film on the wafer described above.
- the insulating film include a silicon oxide film (e.g., silicon dioxide (SiO 2 ) film, tetraethyl orthosilicate (Si(OC 2 H 5 ) 4 ) film (TEOS film), etc.), a silicon nitride film (e.g., , silicon nitride (Si 3 N 4 ), and silicon nitride carbide (SiNC)) and low dielectric constant (Low-k) films such as carbon-doped silicon oxide (SiOC) films and silicon carbide (SiC ) membrane, etc.).
- a low dielectric constant (Low-k) film is preferable.
- the metal inclusion is also preferably a metal film containing metal.
- the metal film of the semiconductor substrate is preferably a metal film containing metal M, and a metal film containing at least one metal selected from the group consisting of Cu, Co, W, Mo, Ru, Al, Ti, and Ta. is more preferred, a metal film containing at least one metal selected from the group consisting of Cu, Co, W, Mo and Ru is more preferred, and a metal film containing Cu is particularly preferred.
- the metal film containing at least one metal selected from the group consisting of Cu, Co, W, Mo, and Ru include a film containing Cu as a main component (a Cu-containing film) and a film containing Co as a main component. films (Co-containing films), films containing W as the main component (W-containing films), films containing Mo as the main component (Mo-containing films), and films containing Ru as the main component (Ru-containing films). .
- the Cu-containing film examples include a wiring film (Cu wiring film) composed only of metal Cu, and an alloy wiring film (Cu alloy wiring film) composed of metal Cu and another metal.
- the Cu alloy wiring film includes an alloy wiring film composed of one or more metals selected from Al, Ti, Cr, Mn, Ta, and W and Cu. More specifically, a CuAl alloy wiring film, a CuTi alloy wiring film, a CuCr alloy wiring film, a CuMn alloy wiring film, a CuTa alloy wiring film, and a CuW alloy wiring film can be mentioned.
- the Co-containing film includes, for example, a metal film composed only of metal Co (Co metal film) and an alloy metal film composed of metal Co and another metal (Co alloy metal film).
- Co alloy metal films include alloy metal films composed of Co and one or more metals selected from Ti, Cr, Fe, Ni, Mo, Pd, Ta, and W. More specifically, a CoTi alloy metal film, a CoCr alloy metal film, a CoFe alloy metal film, a CoNi alloy metal film, a CoMo alloy metal film, a CoPd alloy metal film, a CoTa alloy metal film, and a CoW alloy metal film can be mentioned. .
- Co metal films are often used as wiring films, and Co alloy metal films are often used as barrier metals.
- W-containing film for example, a metal film composed only of W (W metal film) and an alloy metal film composed of W and other metals (W alloy metal film ).
- W alloy metal films include, for example, WTi alloy metal films and WCo alloy metal films.
- a W-containing film is used, for example, as a barrier metal or as a connection between a via and a wire.
- Mo-containing films include, for example, a metal film composed only of metal Mo (Mo metal film) and an alloy metal film composed of metal Mo and other metals (Mo alloy metal film).
- Ru-containing film examples include a metal film made of only metal Ru (Ru metal film) and an alloy metal film made of metal Ru and another metal (Ru alloy metal film). Ru-containing films are often used as barrier metals.
- the cleaning composition has a Cu-containing wiring film and a metal film (Co barrier metal), which is a barrier metal for the Cu-containing wiring film and which is composed only of metal Co, on the upper part of the wafer constituting the semiconductor substrate.
- a metal film Co barrier metal
- the Cu-containing film, the Co-containing film, the W-containing film, the Mo-containing film, and the Ru-containing film on the wafer that constitutes the semiconductor substrate a method usually used in this field is used. There are no particular restrictions.
- a method for forming the insulating film for example, a wafer constituting a semiconductor substrate is subjected to heat treatment in the presence of oxygen gas to form a silicon oxide film, and then silane and ammonia gases are introduced to perform chemical treatment.
- a method of forming a silicon nitride film by chemical vapor deposition (CVD) can be used.
- a method for forming a Cu-containing film, a Co-containing film, a W-containing film, a Mo-containing film, and a Ru-containing film for example, a circuit is formed on a wafer having the insulating film by a known method such as resist. Then, a method of forming a Cu-containing film, a Co-containing film, a W-containing film, a Mo-containing film, and a Ru-containing film by methods such as plating and CVD.
- the object to be cleaned with the cleaning composition is preferably a semiconductor substrate having a metal film after CMP treatment.
- CMP processing for example, the surface of a substrate having a metal wiring film, a barrier metal, and an insulating film is flattened by a combined action of chemical action and mechanical polishing using a polishing slurry containing polishing fine particles (abrasive grains). It is a process to convert Abrasive grains (for example, silica, alumina, etc.) used in the CMP process, polished metal wiring films, and metal impurities (metal residues, especially , Cu-containing metal residue) may remain. Moreover, organic residues derived from the CMP treatment liquid used in the CMP treatment may remain.
- These impurities may cause, for example, short-circuiting between wirings and degrade the electrical characteristics of the semiconductor substrate.
- the semiconductor substrate subjected to the CMP process the Journal of the Society for Precision Engineering Vol. 84, No. 3, 2018, but not limited thereto.
- the surface of the semiconductor substrate to be cleaned with the cleaning composition may be buffed after being subjected to CMP.
- Buffing is a process that uses a polishing pad to reduce impurities on the surface of a semiconductor substrate. Specifically, the surface of the semiconductor substrate subjected to the CMP treatment is brought into contact with the polishing pad, and the semiconductor substrate and the polishing pad are slid relative to each other while supplying the buffing composition to the contact portion. As a result, impurities on the surface of the semiconductor substrate are removed by the frictional force of the polishing pad and the chemical action of the buffing composition.
- a known buffing composition can be appropriately used depending on the type of semiconductor substrate and the type and amount of impurities to be removed.
- Components contained in the buffing composition are not particularly limited, and examples thereof include a water-soluble polymer such as polyvinyl alcohol, water as a dispersion medium, and an acid such as nitric acid.
- the polishing apparatus, polishing conditions, and the like used in the buffing process can be appropriately selected from known apparatuses and conditions according to the type of semiconductor substrate, the object to be removed, and the like.
- Buffing treatments include, for example, the treatments described in paragraphs [0085] to [0088] of WO2017/169539, the contents of which are incorporated herein.
- the buffing treatment it is also preferable to apply the buffing treatment to the semiconductor substrate using the above cleaning composition as the buffing composition. That is, it is also preferable to use the cleaning composition for buffing a semiconductor substrate having a metal film after CMP as an object to be cleaned.
- washing method A method for cleaning a semiconductor substrate using the cleaning composition will be described below. As one mode of the cleaning method, a method for cleaning a semiconductor substrate after CMP treatment will be described.
- the washing method is not limited to the embodiments described below, and may be carried out in an appropriate manner according to the above uses, for example.
- the cleaning method using the cleaning composition is not particularly limited as long as it includes a cleaning step of cleaning a semiconductor substrate subjected to CMP processing.
- the method for cleaning a semiconductor substrate preferably includes a step of applying the diluted cleaning composition obtained in the above dilution step to a semiconductor substrate that has been subjected to a CMP treatment for cleaning.
- the cleaning step of cleaning the semiconductor substrate using the cleaning composition is not particularly limited as long as it is a known method performed on the semiconductor substrate that has been subjected to CMP treatment, and while supplying the cleaning composition to the semiconductor substrate, a brush or the like is applied.
- Scrub cleaning in which a cleaning member is brought into physical contact with the surface of the semiconductor substrate to remove residues, etc.
- immersion cleaning in which the semiconductor substrate is immersed in the cleaning composition
- spin (dripping) method in which the cleaning composition is dropped while rotating the semiconductor substrate.
- a spray method for spraying a cleaning composition may be appropriately adopted.
- immersion-type cleaning it is preferable to apply ultrasonic treatment to the cleaning composition in which the semiconductor substrate is immersed, in order to further reduce impurities remaining on the surface of the semiconductor substrate.
- the washing step may be performed only once, or may be performed twice or more. When washing twice or more, the same method may be repeated, or different methods may be combined.
- the single wafer method is generally a method of processing semiconductor substrates one by one
- the batch method is generally a method of simultaneously processing a plurality of semiconductor substrates.
- the temperature of the cleaning composition used for cleaning semiconductor substrates is not particularly limited as long as it is the temperature normally used in this field. Cleaning is generally performed at room temperature (approximately 25° C.), but the temperature can be arbitrarily selected in order to improve cleaning performance and prevent damage to members.
- the temperature of the cleaning composition is preferably 10-60°C, more preferably 15-50°C.
- the cleaning time in cleaning the semiconductor substrate is not particularly limited, but from a practical point of view, it is preferably 10 seconds to 2 minutes, more preferably 20 seconds to 1 minute 30 seconds, and even more preferably 30 seconds to 1 minute.
- the supply amount (supply rate) of the cleaning composition in the semiconductor substrate cleaning process is not particularly limited, but is preferably 50 to 5000 mL/min, more preferably 500 to 2000 mL/min.
- mechanical agitation methods may be used to further enhance the cleaning ability of the cleaning composition.
- mechanical stirring methods include a method of circulating the cleaning composition over the semiconductor substrate, a method of flowing or spraying the cleaning composition over the semiconductor substrate, and stirring the cleaning composition with ultrasonic waves or megasonics. and the like.
- a step of cleaning the semiconductor substrate by rinsing it with a solvent may be performed.
- the rinsing step is preferably performed continuously after the cleaning step of the semiconductor substrate, and is a step of rinsing using a rinsing solvent (rinsing liquid) for 5 seconds to 5 minutes.
- the rinsing step may be performed using the mechanical agitation method described above.
- rinse liquids examples include water (preferably deionized water), methanol, ethanol, isopropyl alcohol, N-methylpyrrolidinone, ⁇ -butyrolactone, dimethylsulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate.
- Aqueous rinses with a pH greater than 8.0 may also be utilized.
- the above-described method of bringing the cleaning composition into contact with the semiconductor substrate can be similarly applied.
- a drying step for drying the semiconductor substrate may be performed after the rinsing step.
- the drying method is not particularly limited. Drying methods, IPA (isopropyl alcohol) drying methods, and any combination thereof.
- the cleaning composition may be diluted with a diluent such as water, and then used to clean the semiconductor substrate as a diluted cleaning composition (diluted cleaning composition).
- a diluted cleaning composition is also one form of the cleaning composition of the present invention as long as it satisfies the requirements of the present invention.
- the dilution ratio of the diluted cleaning composition may be appropriately adjusted according to the type and content of each component, and the semiconductor substrate or the like to be cleaned.
- the ratio (dilution ratio) of the diluted cleaning composition to the cleaning composition before dilution (dilution ratio) is preferably 10 to 10,000 times, more preferably 20 to 3,000 times, more preferably 50 to 50 times by mass or volume (volume ratio at 23°C). 1000 times is more preferable.
- the cleaning composition is preferably diluted with water in terms of suppressing defects. That is, a cleaning composition (diluted cleaning composition ) can also be suitably put into practical use.
- a cleaning composition diluted cleaning composition
- the preferred content of each component (excluding water) relative to the total mass of the diluted cleaning composition is described as the preferred content of each component relative to the total mass of the cleaning composition (cleaning composition before dilution). It is the amount obtained by dividing the amount by the dilution ratio (for example, 100) in the above range.
- a specific method for the dilution step of diluting the cleaning composition may be carried out according to the method for preparing the cleaning composition described above.
- the stirring device and stirring method used for dilution may also be carried out using the known stirring device mentioned in the cleaning composition preparation method described above.
- the water used for dilution is preferably purified in advance. Further, it is preferable to subject the diluted cleaning composition obtained by dilution to purification treatment.
- the purification treatment includes ion component reduction treatment using an ion exchange resin or RO membrane, and foreign matter removal using filtering, which were described as the purification treatment above. It is preferable to perform any one of these treatments.
- the cleaning method of cleaning a semiconductor substrate using the cleaning composition of the present invention can be suitably used when manufacturing semiconductor elements. That is, the present invention also relates to methods for manufacturing semiconductor devices, including cleaning methods for cleaning semiconductor substrates using cleaning compositions.
- Example 101 citric acid, HEDPO, a sulfonic acid-based surfactant, and water were mixed so as to have the contents shown in Table 1 to form a mixed solution, and then the mixed solution was sufficiently stirred with a stirrer. , to obtain the cleaning composition of Example 101.
- the sulfonic acid-based surfactants were mixed at the ratios shown in Table 1 and mixed so that the contents shown in Table 1 were obtained.
- the compositions of Examples 102 to 121, the compositions of Examples 201 to 204, and Comparative Example 1 were prepared in the same manner as in Example 101, except that the types and amounts of each component were changed according to Table 1 or 2. -4 compositions were made.
- the copper ion concentration contained in the composition is 0.2 mass ppb relative to the total mass of the composition, and the phosphate ion concentration contained in the composition is relative to the total mass of the composition. Filtration treatment was repeated so that the total concentration of 0.001% by mass was obtained.
- the copper ion concentration was confirmed by ICP-MS (Agilent 8800 triple quadrupole ICP-MS (for semiconductor analysis, option #200)). Specifically, a quartz torch, a coaxial PFA nebulizer (for self-priming) and a platinum interface cone were used as the sample introduction system.
- the measurement parameters for the cool plasma conditions were as follows.
- Citric acid 30 Mass % Citric Acid Aqueous Solution
- the citric acid content shown in Tables 1 and 2 is the content of citric acid itself relative to the total weight of the cleaning composition, and the water in the aqueous solution is not included in the citric acid content.
- HEDPO 60% by mass aqueous solution of 1-hydroxyethane-1,1-diphosphonic acid
- the HEDPO content shown in Tables 1 and 2 is the content of HEDPO itself with respect to the total mass of the cleaning composition, and the water in the aqueous solution is included in the HEDPO content. exclude.
- pH The pH of the cleaning composition was measured at 25° C. using a pH meter (F-51 (trade name) manufactured by Horiba, Ltd.).
- the electrical conductivity of the cleaning composition was measured at 25° C. using an electrical conductivity meter (portable type D-70/ES-70 series, manufactured by Horiba, Ltd.).
- a semiconductor substrate after CMP processing was prepared as an object to be cleaned.
- a semiconductor substrate after CMP processing was prepared by the following procedure.
- a wafer (8 inches in diameter) having a metal film made of copper on its surface was polished using a FREX300S-II (polishing machine, manufactured by Ebara Corporation). Polishing was performed using CSL9044C and BSL8176C (trade names, both manufactured by Fuji Film Planar Solutions) as polishing liquids.
- polishing pressure was 2.0 psi
- the supply rate of the polishing liquid was 0.28 mL/(min ⁇ cm 2 ).
- Polishing time was 60 seconds. Thereafter, the CMP-processed wafers were scrub-cleaned for 30 seconds using the cleaning compositions of each example and each comparative example adjusted to room temperature (23° C.), and then dried. Using a defect detector (ComPlus-II, manufactured by AMAT) on the wafer after drying, the number of detected signal intensities corresponding to defects with a length of 0.1 ⁇ m or more is measured on the polished surface of the wafer.
- ComPlus-II manufactured by AMAT
- the residue removability of the cleaning composition was evaluated according to the following evaluation criteria. Results are shown in Tables 1 and 2. It can be evaluated that the smaller the number of defects due to residues detected on the polished surface of the wafer, the better the residue removability. In addition, the residue removability is preferably 3 or more for practical use. Residue removability was evaluated according to the following criteria.
- the number of defects per wafer is less than 280 7: The number of defects per wafer is 280 or more and less than 320 6: The number of defects per wafer is 320 or more and less than 360 5: The number of defects per wafer is 360 or more and less than 400 4: The number of defects per wafer is 400 or more and less than 440 3: The number of defects per wafer is 440 or more and less than 480 2: The number of defects per wafer is 480 or more and less than 500 1: The number of defects per wafer is 500 or more
- a wafer (12 inches in diameter) having a metal film made of copper on its surface was cut to prepare 2 cm square wafer coupons.
- the thickness of the metal film was set to 200 nm.
- a wafer coupon was immersed in the cleaning composition (temperature: 23° C.) of each example and each comparative example, and the stirring speed of the stirrer was set to 250 rpm, and the immersion treatment was performed for 3 minutes.
- the copper content in the cleaning compositions was measured by ICP-MS (Agilent 8800 triple quadrupole ICP-MS (for semiconductor analysis, option #200)) before and after the soak treatment.
- the detailed measurement conditions are the same as those for the measurement of copper ions in the cleaning composition.
- a corrosion rate per unit time (unit: ⁇ /min) was calculated from the obtained measurement results.
- the copper corrosion resistance of the cleaning composition was evaluated according to the evaluation criteria below. Results are shown in Tables 1 and 2. It should be noted that the lower the corrosion rate, the better the anti-corrosion performance of the cleaning composition.
- the copper corrosion resistance is preferably 4 or more for practical use.
- Corrosion rate is less than 1.1 ⁇ /min 7: Corrosion rate is 1.1 ⁇ /min or more and less than 1.4 ⁇ /min 6: Corrosion rate is 1.4 ⁇ /min or more and less than 1.7 ⁇ /min 5: Corrosion Rate is 1.7 ⁇ /min or more and less than 2.0 ⁇ /min 4: Corrosion rate is 2.0 ⁇ /min or more and less than 2.3 ⁇ /min 3: Corrosion rate is 2.3 ⁇ /min or more and 2.6 ⁇ /min Less than 2: Corrosion rate is 2.6 ⁇ /min or more and less than 3.0 ⁇ /min 1: Corrosion rate is 3.0 ⁇ /min or more
- each notation is as follows.
- the description of "remainder” in the "water” column means that the total amount of each component contained in each composition described in the tables was 100% by mass. indicates that In Tables 1 and 2, the “Citric acid (A) wt%” column represents the content (mass%) of citric acid relative to the total mass of the cleaning composition, and the “HEDPO (B) wt%” column represents the cleaning composition. The content (% by mass) of HEDPO with respect to the total mass is shown, and the “content (wt%)” column in the “sulfonic acid surfactant (C)” column indicates the sulfonic acid surfactant relative to the total mass of the cleaning composition. represents the content (% by mass).
- the "LAS-10 (wt%)" column in the “ratio” column of the “sulfonic acid surfactant (C)” column is the total mass of the sulfonic acid surfactants (sulfonic acids A to D). represents the content of LAS-10 (% by mass), and the “LAS-11 (wt%)” column shows the content of LAS-11 with respect to the total mass of sulfonic acid surfactants (sulfonic acids A to D) ( %), and the column “LAS-12 (wt%)” represents the content (% by mass) of LAS-12 with respect to the total mass of sulfonic acid-based surfactants (sulfonic acids A to D), and "LAS -13 (wt%)” column represents the content (% by mass) of LAS-13 with respect to the total mass of the sulfonic acid-based surfactants (sulfonic acids A to D).
- the notation “A/B” represents the mass ratio of the citric acid content to the HEDPO content in the cleaning composition.
- the notation “A/C” represents the mass ratio of the content of citric acid to the total mass of the sulfonic acid-based surfactants contained in the cleaning composition.
- the cleaning composition of the present invention is excellent in residue removability and copper corrosion resistance. From a comparison between Example 105 and Examples 201 to 204, ABS1 containing an alkyl group having 10 carbon atoms, ABS2 containing an alkyl group having 11 carbon atoms, ABS3 containing an alkyl group having 12 carbon atoms, and ABS3 containing an alkyl group having 13 carbon atoms. It was confirmed that the residue removability and the copper corrosion resistance are more excellent when the ABS4 containing the alkyl group of is included.
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Abstract
Description
このような残渣を除去する洗浄液として、例えば、特許文献1には、架橋構造を有する有機重合体粒子、および、界面活性剤を有する洗浄液が開示されている。
また、本発明は、半導体基板の洗浄方法、および、半導体素子の製造方法の提供も課題とする。
1-ヒドロキシエタン-1,1-ジホスホン酸と、
スルホン酸系界面活性剤と、
水と、を含み、
上記1-ヒドロキシエタン-1,1-ジホスホン酸の含有量に対する上記クエン酸の含有量の質量比が20~150であり、
上記スルホン酸系界面活性剤の含有量に対する上記クエン酸の含有量の質量比が70~1500であり、
pHが0.10~4.00である、洗浄組成物。
〔2〕 上記スルホン酸系界面活性剤が、アルキルベンゼンスルホン酸系界面活性剤を含む、〔1〕に記載の洗浄組成物。
〔3〕 上記アルキルベンゼンスルホン酸系界面活性剤が、アルキル基の炭素数が8以上であるアルキルベンゼンスルホン酸系界面活性剤を含む、〔2〕に記載の洗浄組成物。
〔4〕 上記アルキルベンゼンスルホン酸系界面活性剤が、アルキル基の炭素数が10~13であるアルキルベンゼンスルホン酸系界面活性剤を含む、〔2〕または〔3〕に記載の洗浄組成物。
〔5〕 上記スルホン酸系界面活性剤が、
炭素数10のアルキル基を含むアルキルベンゼンスルホン酸系界面活性剤1と、
炭素数11のアルキル基を含むアルキルベンゼンスルホン酸系界面活性剤2と、
炭素数12のアルキル基を含むアルキルベンゼンスルホン酸系界面活性剤3と、
炭素数13のアルキル基を含むアルキルベンゼンスルホン酸系界面活性剤4と、を含む、〔1〕~〔4〕のいずれか1つに記載の洗浄組成物。
〔6〕 上記アルキルベンゼンスルホン酸系界面活性剤1~4の合計質量に対する上記アルキルベンゼンスルホン酸系界面活性剤2の含有量が、20~50質量%である、〔5〕に記載の洗浄組成物。
〔7〕 上記1-ヒドロキシエタン-1,1-ジホスホン酸の含有量に対する上記クエン酸の含有量の質量比が30~100である、〔1〕~〔6〕のいずれか1つに記載の洗浄組成物。
〔8〕 上記1-ヒドロキシエタン-1,1-ジホスホン酸の含有量に対する上記クエン酸の含有量の質量比が40~80である、〔1〕~〔7〕のいずれか1つに記載の洗浄組成物。
〔9〕 上記1-ヒドロキシエタン-1,1-ジホスホン酸の含有量に対する上記クエン酸の含有量の質量比が50~60である、〔1〕~〔8〕のいずれか1つに記載の洗浄組成物。
〔10〕 上記スルホン酸系界面活性剤の含有量に対する上記クエン酸の含有量の質量比が200~600である、〔1〕~〔9〕のいずれか1つに記載の洗浄組成物。
〔11〕 上記スルホン酸系界面活性剤の含有量に対する上記クエン酸の含有量の質量比が300~500である、〔1〕~〔10〕のいずれか1つに記載の洗浄組成物。
〔12〕 上記スルホン酸系界面活性剤の含有量に対する上記クエン酸の含有量の質量比が410~440である、〔1〕~〔11〕のいずれか1つに記載の洗浄組成物。
〔13〕 洗浄組成物全質量に対する上記クエン酸の含有量が、0.1~35.0質量%である、〔1〕~〔12〕のいずれか1つに記載の洗浄組成物。
〔14〕 洗浄組成物全質量に対する上記クエン酸の含有量が、1.0~35.0質量%である、〔1〕~〔13〕のいずれか1つに記載の洗浄組成物。
〔15〕 洗浄組成物全質量に対する上記クエン酸の含有量が、20.0~35.0質量%である、〔1〕~〔14〕のいずれか1つに記載の洗浄組成物。
〔16〕 〔1〕~〔15〕のいずれか1つに記載の洗浄組成物を用いて半導体基板を洗浄する、半導体基板の洗浄方法。
〔17〕 〔16〕に記載の半導体基板の洗浄方法を含む、半導体素子の製造方法。
また、本発明によれば、半導体基板の洗浄方法、および、半導体素子の製造方法を提供できる。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされる場合があるが、本発明はそのような実施態様に制限されない。
本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
本明細書においてppmとは“parts per million”の略であり、10-6を意味する。また、本明細書においてppbとは“parts per billion”の略であり、10-9を意味する。
本明細書において、「psi」とは、“pound-force per square inch”、すなわち重量ポンド毎平方インチを意味し、1psi=6894.76Paを意味する。
本明細書に記載の化合物において、特段の断りがない限り、異性体(原子数が同じであるが構造が異なる化合物)、光学異性体および同位体が含まれていてもよい。また、異性体および同位体は、1種のみが含まれていてもよいし、複数種含まれていてもよい。
本明細書において、ある成分が2種以上存在する場合、その成分の「含有量」は、それら2種以上の成分の合計含有量を意味する。
本発明の洗浄組成物は、クエン酸と、1-ヒドロキシエタン-1,1-ジホスホン酸(以下、「HEDPO」ともいう。)と、スルホン酸系界面活性剤と、水と、を含み、HEDPOの含有量に対するクエン酸の含有量の質量比が20~150であり、スルホン酸系界面活性剤の含有量に対するクエン酸の含有量の質量比が70~1500であり、pHが0.10~4.00である。
以下、洗浄組成物が含む成分、洗浄組成物の性状、および、洗浄組成物の調製について詳述する。
本発明の洗浄組成物は、クエン酸と、1-ヒドロキシエタン-1,1-ジホスホン酸(HEDPO)と、スルホン酸系界面活性剤と、水と、を含む。また、本発明の洗浄組成物は、後述するその他成分を含んでいてもよい。
以下、洗浄組成物が含む各成分、および、成分の含有質量比について詳述する。
クエン酸は、不純物含有量が少ないことが好ましく、例えば、半導体グレードのものが好ましい。
洗浄組成物全質量に対するクエン酸の含有量は、残渣の除去性および銅の防食性がより優れる点で、0.1~35.0質量%が好ましく、1.0~35.0質量%がより好ましく、20.0~35.0質量%がさらに好ましい。
1-ヒドロキシエタン-1,1-ジホスホン酸(HEDPO)は、不純物含有量が少ないことが好ましく、例えば、半導体グレードのものが好ましい。
洗浄組成物全質量に対するHEDPOの含有量は、0.001~5.0質量%が好ましく、0.01~2.0質量%がより好ましく、0.1~1.0質量%がさらに好ましく、0.4~0.8質量%が特に好ましい。
スルホン酸系界面活性剤とは、界面活性剤分子が有する疎水基と親水基とのうち、親水基にスルホ基を含む界面活性剤である。
スルホン酸系界面活性剤における疎水基は特に制限されず、例えば、脂肪族炭化水素基、芳香族炭化水素基、および、それらの組合せが挙げられる。疎水基の炭素数は、6以上が好ましく、10以上がより好ましい。疎水基の炭素数の上限は特に制限されないが、24以下が好ましく、20以下がより好ましい。
アルキルアリールスルホン酸系界面活性剤が有するアルキル基は直鎖状、および、分岐鎖状のどちらであってもよく、分岐鎖状が好ましい。上記アルキル基の炭素数は、8以上が好ましく、8~20がより好ましく、10~13がさらに好ましい。
アルキルアリールスルホン酸系界面活性剤が含む芳香族炭化水素環としては、例えば、ベンゼン環、および、ナフタレン環が挙げられる。
アルキルアリールスルホン酸系界面活性剤が有するスルホ基は、芳香族炭化水素環に直接結合していることが好ましい。スルホ基は、カチオンと塩を形成していてもよい。
アルキルアリールスルホン酸系界面活性剤としては、式(A)で表される界面活性剤が好ましい。
Ra-Ara-SO3H (A)
式(A)中、Raは、炭素数8以上のアルキル基を表す。Araは、アリーレン基を表す。
上記アルキル基の炭素数の好適範囲は、上述した通りである。
上記アリーレン基は、単環および多環のいずれであってもよい。アリーレン基の炭素数は、6~20が好ましく、6~15がより好ましい。
アリーレン基としては、フェニレン基またはナフチレン基が好ましい。
なお、以下、アルキルベンゼンスルホン酸系界面活性剤のことを「ABS」ともいう。
ABSが有するアルキル基は直鎖状、および、分岐鎖状のどちらであってもよく、分岐鎖状が好ましい。ABSが有するアルキル基の炭素数は、8以上が好ましく、8~20がより好ましく、10~13がさらに好ましい。
ABSとしては、式(A)中のAraがフェニレン基である態様が挙げられる。
ABS1としては、式(A)中のAraがフェニレン基であり、Raが炭素数10のアルキル基である態様が挙げられる。ABS2としては、式(A)中のAraがフェニレン基であり、Raが炭素数11のアルキル基である態様が挙げられる。ABS3としては、式(A)中のAraがフェニレン基であり、Raが炭素数12のアルキル基である態様が挙げられる。ABS4としては、式(A)中のAraがフェニレン基であり、Raが炭素数13のアルキル基である態様が挙げられる。
ABS1~4の合計質量に対するABS1の含有量は、特に制限されないが、5~50質量%が好ましい。
ABS1~4の合計質量に対するABS2の含有量は、特に制限されないが、20~50質量%が好ましい。
ABS1~4の合計質量に対するABS3の含有量は、特に制限されないが、20~50質量%が好ましい。
ABS1~4の合計質量に対するABS4の含有量は、特に制限されないが、20~50質量%が好ましい。
水としては、蒸留水、イオン交換水、および、超純水等の浄化処理を施された水が好ましく、半導体製造に使用される超純水がより好ましい。
洗浄組成物全質量に対する水の含有量は、50.00~99.99質量%が好ましく、60.00~98.00質量%がより好ましく、65.00~85.00質量%がさらに好ましく、68.00~75.00質量%が特に好ましい。
洗浄組成物が含んでいてもよいその他成分としては、例えば、金属イオン、リン酸イオン、無機粒子、有機粒子、アミン化合物、防食剤、および、pH調整剤が挙げられる。他にも、スルホン酸系界面活性剤以外の界面活性剤を含んでいてもよい。
洗浄組成物が金属イオンを含む場合、金属イオンの金属元素としては、Fe、Co、Na、Cu、Mg、Mn、Li、Al、Cr、Ni、Zn、Sn、および、Agが挙げられる。
洗浄組成物全質量に対する銅イオンの含有量は、0.5質量ppb以下が好ましい。下限は特に制限されないが、検出されないことが好ましい。
金属イオンの含有量は公知の方法で求めることができ、例えば、ICP-MS(Inductively Coupled Plasma-Mass Spectrometry)が挙げられる。本明細書において、金属イオンの含有量は、ICP-MSで測定して得られたものとする。
洗浄組成物がリン酸イオンを含む場合、洗浄組成物全質量に対するリン酸イオンの含有量は、1.0質量%以下が好ましく、0.1質量%以下がより好ましく、0.01質量%以下がさらに好ましい。
洗浄組成物中においてリン酸イオンは検出されないことが好ましいが、洗浄組成物全質量に対するリン酸イオンの含有量は、0.001質量%以上の場合が多い。
リン酸イオンは公知の方法で求めることができ、例えば、イオンクロマトグラフィー、および、モリブデン酸アンモニウムを用いる比色法が挙げられる。
上記リン酸イオンの含有量を調整する方法としては、例えば、洗浄組成物中に含まれる成分および調整後の洗浄組成物を、蒸留およびイオン交換樹脂等を用いて精製する方法が挙げられる。
洗浄組成物が無機粒子および有機粒子の少なくとも一方を含む場合、洗浄組成物全質量に対する無機粒子および有機粒子の合計含有量は、1.0質量%以下が好ましく、0.1質量%以下がより好ましく、0.01質量%以下がさらに好ましい。下限は特に制限されないが、0.1質量ppb以上が挙げられる。
洗浄組成物に含まれる無機粒子および有機粒子は、原料に不純物として含まれる有機固形物および無機固形物等の粒子、ならびに、洗浄組成物の調製中に汚染物として持ち込まれる有機固形物および無機固形物等の粒子であって、最終的に洗浄組成物中で溶解せずに粒子として存在するものが該当する。
洗浄組成物中に存在する無機粒子および有機粒子の含有量は、レーザを光源とした光散乱式液中粒子測定方式における市販の測定装置を利用して液相で測定できる。
無機粒子および有機粒子の除去方法としては、例えば、後述するフィルタリング等の精製処理が挙げられる。
アミン化合物は、アミノ基を有する化合物である。上記アミン化合物が有するアミノ基は、第1級のアミノ基(-NH2)、第2級のアミノ基(>NH)および第3級のアミノ基(>N-)からなる群から選択される少なくとも1つのアミノ基である。なお、アミン化合物が、複数の級数のアミノ基を有する場合、そのうち最も高級なアミノ基を有するアミン化合物に分類する。具体的には、第1級のアミノ基と、第2級のアミン基とを有するアミン化合物は、第2級のアミン基を有するアミン化合物とする。
アミン化合物としては、例えば、脂肪族アミンおよびアミノアルコール(ヒドロキシ基を有する脂肪族アミン)が挙げられる。上記アミン化合物は、鎖状(直鎖状または分岐鎖状)および環状のいずれであってもよい。
アミン化合物は、1種単独または2種以上で用いてもよい。
防食剤としては、例えば、ヘテロ原子を有する化合物が挙げられ、複素環を有する化合物(複素環化合物)が好ましく、多環の複素環を有する化合物がより好ましい。
防食剤としては、プリン化合物、アゾール化合物または還元性硫黄化合物が好ましい。
防食剤は、洗浄組成物に含まれ得る上記化合物とは異なる化合物であることが好ましい。
防食剤は、1種単独または2種以上で用いてもよい。
洗浄組成物が防食剤を含む場合、洗浄組成物全質量に対する防食剤の含有量は、0.01~10.0質量%が好ましく、1.0~10.0質量%がより好ましく、5.0~8.0質量%が更に好ましい。
他の界面活性剤としては、1分子中に親水基と疎水基(親油基)とを有する化合物であり、例えば、ノニオン性界面活性剤、アニオン性界面活性剤、カチオン性界面活性剤および両性界面活性剤が挙げられる。
洗浄組成物が他の界面活性剤を含む場合、金属膜の防食性能および研磨微粒子の除去性がより優れる。
他の界面活性剤としては、例えば、特開2015-158662号公報の段落[0092]~[0096]、特開2012-151273号公報の段落[0045]~[0046]および特開2009-147389号公報の段落[0014]~[0020]に記載の化合物も挙げられ、これらの内容は本明細書に組み込まれる。
他の界面活性剤は、1種単独または2種以上で用いてもよい。
洗浄組成物が他の界面活性剤を含む場合、洗浄組成物全質量に対する他の界面活性剤の含有量は、0.001~8.0質量%が好ましく、0.005~5.0質量%がより好ましく、0.01~3.0質量%が更に好ましい。
pH調整剤は、洗浄組成物に含まれ得る上記化合物とは異なる、塩基性化合物または酸性化合物である。
pH調整剤としては、例えば、第4級アンモニウム化合物、塩基性化合物、および、酸性化合物が挙げられ、第4級アンモニウム化合物、硫酸、または、水酸化カリウムが好ましい。
上述した各成分の添加量を調整することで、洗浄組成物のpHを調整してもよい。
pH調整剤としては、例えば、国際公開第2019-151141号の段落[0053]および[0054]、ならびに、国際公開第2019-151001号の段落[0021]が挙げられ、これらの内容は本明細書に組み込まれる。
洗浄組成物がpH調整剤を含む場合、洗浄組成物全質量に対するpH調整剤の含有量は、その他成分の種類および量に応じて選択でき、0.01~10.0質量%が好ましく、0.05~5.0質量%がより好ましく、0.05~3.0質量%が更に好ましい。
以下、本発明の洗浄組成物の性状を説明する。具体的には、pH、電気伝導度、および、粗大粒子について説明する。
本発明の洗浄組成物のpHは、0.10~4.00である。
洗浄組成物のpHは、銅の防食性がより優れる点で、0.50~3.00が好ましく、1.00~2.00がより好ましく、1.00~1.50がさらに好ましい。
本明細書において、洗浄組成物のpHは、25℃において、pHメーター(株式会社堀場製作所製、F-51(商品名))を用いて測定することにより得られる。
pHの調整方法としては、例えば、洗浄組成物に含まれ得る各成分の種類および含有量を調整する方法、ならびに、上述したpH調整剤を添加する方法が挙げられる。
洗浄組成物の電気伝導度は、0.05~11.0mS/cmが好ましい。
洗浄組成物の電気伝導度は、1.00~11.0mS/cmがより好ましく、4.00~11.0mS/cmがさらに好ましい。
本明細書において、洗浄組成物の電気伝導度は、25℃において、電気伝導率計(ポータブル型D-70/ES-70シリーズ、堀場製作所社製)を用いて測定することにより得られる。
上記電気伝導度を調整する方法としては、例えば、洗浄組成物に含まれ得る各成分の種類および含有量を調整する方法が挙げられる。
以下、本発明の洗浄組成物の製造に関して詳述する。具体的には、調液方法、精製処理、洗浄組成物を収容する容器、および、製造等を行う取り扱い環境について詳述する。
洗浄組成物の調液方法は特に制限されず、例えば、上述した各成分を混合することにより洗浄組成物を製造できる。上述した各成分を混合する順序、および/または、タイミングは特に制限されない。例えば、水に対して、クエン酸、HEDPO、スルホン酸系界面活性剤、および、その他成分を混合する方法、ならびに、クエン酸水溶液に対して、水、HEDPO、スルホン酸系界面活性剤、および、その他成分を混合する方法が挙げられる。
各成分を混合する際、各成分はそれぞれ一括して混合してもよく、複数回に分割して混合してもよい。
なお、混合する各成分は、固体を用いてもよく、水溶液を用いてもよい。
洗浄組成物を製造するための原料のいずれか1種以上に対して、事前に精製処理を行うことが好ましい。また、上記方法で製造した洗浄組成物に対して精製処理を行ってもよい。精製処理としては、特に制限されず、例えば、蒸留、イオン交換、および、ろ過等の公知の方法が挙げられる。
精製の程度としては、特に制限されないが、例えば、原料の純度が99質量%以上となるまで精製することが好ましく、原液の純度が99.9質量%以上となるまで精製することがより好ましい。
精製処理として、上述した精製方法を複数組み合わせて実施してもよい。例えば、原料に対して、RO膜に通液する1次精製を行った後、カチオン交換樹脂、アニオン交換樹脂、または、混床型イオン交換樹脂からなる精製装置に通液する2次精製を実施してもよい。
また、精製処理は、複数回実施してもよい。
洗浄組成物(後述する希釈洗浄組成物の態様を含む)は、腐食性等が問題とならない限り、任意の容器に充填して保管、運搬、および、使用できる。
洗浄組成物を収容する容器は、その収容部の内壁等の洗浄組成物との接液部が、フッ素系樹脂(パーフルオロ樹脂)で形成されたものであるか、防錆処理、および/または、金属溶出防止処理が施された金属で形成されたものが好ましい。
容器の内壁は、樹脂、または、防錆および金属溶出防止処理が施された金属から形成されることが好ましい。樹脂としては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、および、ポリエチレン-ポリプロピレン樹脂からなる群から選択される1種以上の樹脂、ならびに、後述するこれとは異なる樹脂が挙げられる。防錆、および、金属溶出防止処理が施される金属としては、ステンレス、ハステロイ、インコネル、および、モネル等が挙げられる。
このような内壁がフッ素系樹脂である容器の具体例としては、例えば、Entegris社製 FluoroPurePFA複合ドラム等が挙げられる。また、特表平3-502677号公報の第4頁、国際公開第2004/016526号明細書の第3頁、ならびに国際公開第99/46309号明細書の第9頁、および、16頁等に記載の容器も使用できる。
上記電解研磨された金属材料の製造に用いられる金属材料は、クロム、および、ニッケルからなる群から選択される少なくとも1つを含み、クロム、および、ニッケルの含有量の合計が金属材料全質量に対して25質量%超である金属材料であることが好ましく、例えば、ステンレス鋼、および、ニッケル-クロム合金等が挙げられる。
金属材料におけるクロム、および、ニッケルの含有量の合計は、金属材料の全質量に対して30質量%以上がより好ましい。
なお、金属材料におけるクロム、および、ニッケルの含有量の合計の上限値としては特に制限されないが、90質量%以下が好ましい。
洗浄組成物の製造、容器の開封、洗浄、および、洗浄組成物の充填等を含めた取り扱い、処理分析、ならびに、測定は、全てクリーンルームで行うことが好ましい。クリーンルームは、14644-1クリーンルーム基準を満たすことが好ましい。ISO(国際標準化機構)クラス1、ISOクラス2、ISOクラス3、および、ISOクラス4のいずれかを満たすことが好ましく、ISOクラス1またはISOクラス2を満たすことがより好ましく、ISOクラス1を満たすことがさらに好ましい。
洗浄組成物の用途、洗浄対象物、洗浄方法、および、洗浄組成物の使用方法について以下に詳述する。
洗浄組成物は、半導体基板の製造プロセスにおける半導体基板を洗浄する工程に使用することが好ましい。なかでも、洗浄組成物は、化学機械研磨(CMP)処理が施された半導体基板を洗浄する洗浄工程に使用することが好ましい。他にも、洗浄組成物は、後述するようにバフ研磨処理にも使用できる。また、洗浄組成物は、半導体基板の製造プロセスに用いられる装置等の洗浄に使用できる。
後述する通り、半導体基板の洗浄には、洗浄組成物を希釈して得られる希釈洗浄組成物を使用してもよい。
以下、洗浄組成物が好ましく用いられる洗浄対象物について詳述する。
洗浄組成物の洗浄対象物としては、例えば、半導体基板(より具体的には、金属含有物を有する半導体基板)が挙げられる。
洗浄対象物は、後述するCMP処理後の金属含有物を有する半導体基板、および、CMP処理後にバフ研磨を行った金属含有物を有する半導体基板が好ましい。
金属含有物は、これらの化合物のうちの2種以上を含む混合物であってもよい。
なお、上記酸化物、窒化物、および、酸窒化物は、金属を含む、複合酸化物、複合窒化物、および、複合酸窒化物のいずれであってもよい。
金属含有物中の金属原子の含有量は、金属含有物の全質量に対して、10質量%以上が好ましく、30質量%以上がより好ましく、50質量%以上が更に好ましい。上限は、金属含有物が金属そのものであってもよいことから、100質量%以下が好ましい。
シリコンウエハとしては、シリコンウエハに5価の原子(例えば、リン(P)、ヒ素(As)、および、アンチモン(Sb)等)をドープしたn型シリコンウエハ、ならびに、シリコンウエハに3価の原子(例えば、ホウ素(B)、および、ガリウム(Ga)等)をドープしたp型シリコンウエハであってもよい。シリコンウエハのシリコンとしては、例えば、アモルファスシリコン、単結晶シリコン、多結晶シリコン、および、ポリシリコンのいずれであってもよい。
絶縁膜の具体例としては、シリコン酸化膜(例えば、二酸化ケイ素(SiO2)膜、および、オルトケイ酸テトラエチル(Si(OC2H5)4)膜(TEOS膜)等)、シリコン窒化膜(例えば、窒化シリコン(Si3N4)、および、窒化炭化シリコン(SiNC)等)、ならびに、低誘電率(Low-k)膜(例えば、炭素ドープ酸化ケイ素(SiOC)膜、および、シリコンカーバイド(SiC)膜等)が挙げられる。なかでも、低誘電率(Low-k)膜が好ましい。
半導体基板が有する金属膜としては、金属Mを含む金属膜が好ましく、Cu、Co、W、Mo、Ru、Al、Ti、および、Taからなる群から選択される少なくとも1つの金属を含む金属膜がより好ましく、Cu、Co、W、Mo、および、Ruからなる群から選択される少なくとも1つの金属を含む金属膜がさらに好ましく、Cuを含む金属膜が特に好ましい。
Cu、Co、W、Mo、および、Ruからなる群から選択される少なくとも1つの金属を含む金属膜としては、例えば、Cuを主成分とする膜(Cu含有膜)、Coを主成分とする膜(Co含有膜)、Wを主成分とする膜(W含有膜)、Moを主成分とする膜(Mo含有膜)、および、Ruを主成分とする膜(Ru含有膜)が挙げられる。
Cu合金配線膜としては、Al、Ti、Cr、Mn、Ta、および、Wから選ばれる1種以上の金属とCuとからなる合金製の配線膜が挙げられる。より具体的には、CuAl合金配線膜、CuTi合金配線膜、CuCr合金配線膜、CuMn合金配線膜、CuTa合金配線膜、および、CuW合金配線膜が挙げられる。
Co合金金属膜としては、Ti、Cr、Fe、Ni、Mo、Pd、Ta、および、Wから選ばれる1種以上の金属とCoとからなる合金製の金属膜が挙げられる。より具体的には、CoTi合金金属膜、CoCr合金金属膜、CoFe合金金属膜、CoNi合金金属膜、CoMo合金金属膜、CoPd合金金属膜、CoTa合金金属膜、および、CoW合金金属膜が挙げられる。
Co含有膜のうち、Co金属膜は配線膜として使用されることが多く、Co合金金属膜はバリアメタルとして使用されることが多い。
W合金金属膜としては、例えば、WTi合金金属膜、および、WCo合金金属膜が挙げられる。
W含有膜は、例えば、バリアメタル、または、ビアと配線の接続部に使用される。
絶縁膜の形成方法としては、例えば、半導体基板を構成するウエハに対して、酸素ガス存在下で熱処理を行うことによりシリコン酸化膜を形成し、次いで、シランおよびアンモニアのガスを流入して、化学気相蒸着(CVD:Chemical Vapor Deposition)法によりシリコン窒化膜を形成する方法が挙げられる。
Cu含有膜、Co含有膜、W含有膜、Mo含有膜、および、Ru含有膜を形成する方法としては、例えば、上記の絶縁膜を有するウエハ上に、レジスト等の公知の方法で回路を形成し、次いで、めっきおよびCVD法等の方法により、Cu含有膜、Co含有膜、W含有膜、Mo含有膜、および、Ru含有膜を形成する方法が挙げられる。
洗浄組成物の洗浄対象物としては、CMP処理後の金属膜を有する半導体基板が好ましい。
CMP処理は、例えば、金属配線膜、バリアメタル、および、絶縁膜を有する基板の表面を、研磨微粒子(砥粒)を含む研磨スラリーを用いて、化学的作用と機械的研磨の複合作用で平坦化する処理である。
CMP処理が施された半導体基板の表面には、CMP処理で使用した砥粒(例えば、シリカおよびアルミナ等)、研磨された金属配線膜、および、バリアメタルに由来する金属不純物(金属残渣。特に、Cu含有金属残渣)等の不純物が残存することがある。また、CMP処理の際に用いたCMP処理液に由来する有機残渣物が残存する場合もある。これらの不純物は、例えば、配線間を短絡させ、半導体基板の電気的特性を劣化させるおそれがあるため、CMP処理が施された半導体基板は、これらの不純物を表面から除去するための洗浄処理に供される。
CMP処理が施された半導体基板の具体例としては、精密工学会誌 Vol.84、No.3、2018に記載のCMP処理が施された基板が挙げられるが、これに制限されるものではない。
洗浄組成物の洗浄対象物である半導体基板の表面は、CMP処理が施された後、バフ研磨処理が施されていてもよい。
バフ研磨処理は、研磨パッドを用いて半導体基板の表面における不純物を低減する処理である。具体的には、CMP処理が施された半導体基板の表面と研磨パッドとを接触させて、その接触部分にバフ研磨用組成物を供給しながら半導体基板と研磨パッドとを相対摺動させる。その結果、半導体基板の表面の不純物が、研磨パッドによる摩擦力およびバフ研磨用組成物による化学的作用によって除去される。
バフ研磨処理において使用する研磨装置および研磨条件等については、半導体基板の種類および除去対象物等に応じて、公知の装置および条件から適宜選択できる。バフ研磨処理としては、例えば、国際公開第2017/169539号の段落[0085]~[0088]に記載の処理が挙げられ、この内容は本明細書に組み込まれる。
以下、洗浄組成物を用いた半導体基板の洗浄方法について説明する。洗浄方法の一態様として、CMP処理後の半導体基板の洗浄方法について説明する。
洗浄方法は以下に記載する態様に制限されず、例えば、上記用途に応じて適切な方法で実施されてもよい。
上記洗浄工程は、1回のみ実施してもよく、2回以上実施してもよい。2回以上洗浄する場合には同じ方法を繰り返してもよいし、異なる方法を組み合わせてもよい。
機械的撹拌方法としては、例えば、半導体基板上で洗浄組成物を循環させる方法、半導体基板上で洗浄組成物を流過または噴霧させる方法、および、超音波またはメガソニックにて洗浄組成物を撹拌する方法等が挙げられる。
リンス工程は、半導体基板の洗浄工程の後に連続して行われ、リンス溶媒(リンス液)を用いて5秒間~5分間にわたってすすぐ工程であることが好ましい。リンス工程は、上述の機械的撹拌方法を用いて行ってもよい。
リンス液を半導体基板に接触させる方法としては、上述した洗浄組成物を半導体基板に接触させる方法を同様に適用できる。
乾燥方法としては、特に制限されず、例えば、スピン乾燥法、半導体基板上に乾性ガスを流過させる方法、ホットプレートまたは赤外線ランプのような加熱手段によって基板を加熱する方法、マランゴニ乾燥法、ロタゴニ乾燥法、IPA(イソプロピルアルコール)乾燥法、および、それらの任意の組み合わせが挙げられる。
上記洗浄組成物は、水等の希釈剤を用いて希釈した後、希釈された洗浄組成物(希釈洗浄組成物)として半導体基板の洗浄に供されてもよい。
なお、希釈洗浄組成物も、本発明の要件を満たす限り、本発明の洗浄組成物の一形態である。
希釈洗浄組成物の希釈倍率は、各成分の種類および含有量、ならびに、洗浄対象である半導体基板等に応じて適宜調整すればよい。希釈前の洗浄組成物に対する希釈洗浄組成物の比率(希釈倍率)は、質量比または体積比(23℃における体積比)で、10~10000倍が好ましく、20~3000倍がより好ましく、50~1000倍がさらに好ましい。
また、欠陥が抑制できる点で、洗浄組成物は水で希釈されることが好ましい。
つまり、上記洗浄組成物に含まれ得る各成分(水は除く)の好適な含有量を、上記範囲の希釈倍率(例えば100)で除した量で各成分を含む洗浄組成物(希釈洗浄組成物)も好適に実用できる。
換言すると、希釈洗浄組成物の全質量に対する各成分(水は除く)の好適含有量は、例えば、洗浄組成物(希釈前の洗浄組成物)の全質量に対する各成分の好適含有量として説明した量を、上記範囲の希釈倍率(例えば100)で除した量である。
精製処理としては、上記精製処理として記載した、イオン交換樹脂またはRO膜を用いたイオン成分低減処理、および、フィルタリングを用いた異物除去が挙げられる。これらのうち、いずれかの処理を行うことが好ましい。
以下の実施例に示す材料、使用量、割合、処理内容、および、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更できる。したがって、本発明の範囲は以下に示す実施例により限定的に解釈されるべきではない。
実施例101については、クエン酸、HEDPO、スルホン酸系界面活性剤、および、水を表1の含有量となるように混合して混合液とした後、混合液を撹拌機によって十分に撹拌し、実施例101の洗浄組成物を得た。なお、スルホン酸系界面活性剤は、表1に示す割合で各界面活性剤を混合し、表1に示す含有量となるように混合した。
表1または2にしたがって各成分の種類および量を変更した以外は、実施例101と同様の手順で、実施例102~121の組成物、実施例201~204の組成物、および、比較例1~4の組成物を製造した。
なお、組成物は、製造した後、組成物中に含まれる銅イオン濃度が組成物全質量に対して0.2質量ppb、組成物中に含まれるリン酸イオン濃度が組成物全質量に対して0.001質量%となるようにろ過処理を繰り返した。銅イオン濃度はICP-MS(Agilent 8800 トリプル四重極ICP-MS(半導体分析用、オプション#200))で確認した。具体的には、サンプル導入系としては石英のトーチ、同軸型PFAネブライザ(自吸用)及び白金インターフェースコーンを使用した。クールプラズマ条件の測定パラメータは以下の通りであった。
・ RF(Radio Frequency)出力(W):600
・ キャリアガス流量(L/分):0.7
・ メークアップガス流量(L/分):1
・ サンプリング深さ(mm):18
また、リン酸イオンの含有量は、イオン交換クロマトグラフィー(IEC)を用いて測定した。
また、実施例および比較例の洗浄組成物の製造にあたって、容器の取り扱い、洗浄組成物の調液、充填、保管および分析測定は、全てISOクラス2以下を満たすレベルのクリーンルームで行った。
以下に、各組成物の調製に用いた各成分について示す。
30質量%クエン酸水溶液
なお、表1および2に示すクエン酸含有量は、洗浄組成物全質量に対するクエン酸そのものの含有量であり、水溶液の水はクエン酸含有量に含めない。
60質量%1-ヒドロキシエタン-1,1-ジホスホン酸水溶液
なお、表1および2に示すHEDPO含有量は、洗浄組成物全質量に対するHEDPOそのものの含有量であり、水溶液の水はHEDPO含有量に含めない。
LAS-10:スルホン酸A
LAS-11:スルホン酸B
LAS-12:スルホン酸C
LAS-13:スルホン酸D
ANS-11:ANS
超純水
各種評価方法について以下に詳述する。
洗浄組成物のpHは、25℃において、pHメーター(株式会社堀場製作所製、F-51(商品名))を用いて測定した。
洗浄組成物の電気伝導度は、25℃において、電気伝導率計(ポータブル型D-70/ES-70シリーズ、堀場製作所社製)を用いて測定した。
上記製造した洗浄組成物を用いて、化学機械研磨(CMP)処理を施した金属膜を洗浄した際の洗浄性能(残渣除去性)を評価した。残渣除去性の評価は、以下の手順にしたがって行った。
まず、洗浄対象物となるCMP処理後の半導体基板を準備した。具体的には、以下の手順でCMP処理後の半導体基板を準備した。
銅からなる金属膜を表面に有するウエハ(直径8インチ)を、FREX300S-II(研磨装置、(株)荏原製作所製)を用いて研磨した。研磨液としてCSL9044C、および、BSL8176C(商品名、いずれも富士フイルムプラナーソリューションズ社製)をそれぞれ使用して研磨を行った。これにより、研磨液による洗浄性能評価のばらつきを抑えた。上記の各金属膜を表面に有するウエハに対するCMP処理において、研磨圧力は2.0psiであり、研磨液の供給速度は0.28mL/(分・cm2)であった。研磨時間は60秒間であった。
その後、室温(23℃)に調整した各実施例および各比較例の洗浄組成物を用いて、CMP処理されたウエハを30秒間、スクラブ洗浄し、次いで、乾燥処理した。
乾燥処理後のウエハに対して、欠陥検出装置(AMAT社製、ComPlus-II)を用い、ウエハの研磨面において、長さが0.1μm以上である欠陥に対応する信号強度の検出数を計測し、下記の評価基準により洗浄組成物の残渣除去性を評価した。結果を表1および2に示す。
ウエハの研磨面において検出された残渣物による欠陥数が少ないほど、残渣除去性に優れると評価できる。なお、残渣除去性は、実用上、3以上が好ましい。
残渣除去性は、以下の基準にしたがって評価した。
7 :ウエハあたりの欠陥数が280個以上320未満
6 :ウエハあたりの欠陥数が320個以上360未満
5 :ウエハあたりの欠陥数が360個以上400未満
4 :ウエハあたりの欠陥数が400個以上440未満
3 :ウエハあたりの欠陥数が440個以上480未満
2 :ウエハあたりの欠陥数が480個以上500未満
1 :ウエハあたりの欠陥数が500個以上
銅からなる金属膜を表面に有するウエハ(直径12インチ)をカットし、2cm角のウエハクーポンをそれぞれ準備した。金属膜の厚さは200nmとした。
各実施例および各比較例の洗浄組成物(温度:23℃)中にウエハクーポンを浸漬し、スターラーの撹拌回転数を250rpmとし、3分間の浸漬処理を行った。浸漬処理前後で、洗浄組成物中の銅の含有量をICP-MS(Agilent 8800 トリプル四重極ICP-MS(半導体分析用、オプション#200))で測定した。詳細な測定条件は上記洗浄組成物中の銅イオンの測定と同様である。
得られた測定結果から単位時間当たりの腐食速度(単位:Å/分)を算出した。下記の評価基準により洗浄組成物の銅防食性を評価した。結果を表1および2に示す。
なお、腐食速度が低いほど、洗浄組成物の腐食防止性能が優れる。銅防食性は、実用上、4以上が好ましい。
7 :腐食速度が1.1Å/分以上、1.4Å/分未満
6 :腐食速度が1.4Å/分以上、1.7Å/分未満
5 :腐食速度が1.7Å/分以上、2.0Å/分未満
4 :腐食速度が2.0Å/分以上、2.3Å/分未満
3 :腐食速度が2.3Å/分以上、2.6Å/分未満
2 :腐食速度が2.6Å/分以上、3.0Å/分未満
1 :腐食速度が3.0Å/分以上
表1および2中、「水」欄の「残部」の記載は、表中に記載した各組成物に含まれる各成分の合計量が100質量%になるように必要な量の水を使用したことを示す。
表1および2中、「クエン酸(A)wt%」欄は、洗浄組成物全質量に対するクエン酸の含有量(質量%)を表し、「HEDPO(B)wt%」欄は、洗浄組成物全質量に対するHEDPOの含有量(質量%)を表し、「スルホン酸系界面活性剤(C)」欄の「含有量(wt%)」欄は、洗浄組成物全質量に対するスルホン酸系界面活性剤の含有量(質量%)を表す。
表1中、「スルホン酸系界面活性剤(C)」欄の「比率」欄の「LAS-10(wt%)」欄は、スルホン酸系界面活性剤(スルホン酸A~D)の合計質量に対するLAS-10の含有量(質量%)を表し、「LAS-11(wt%)」欄は、スルホン酸系界面活性剤(スルホン酸A~D)の合計質量に対するLAS-11の含有量(質量%)を表し、「LAS-12(wt%)」欄は、スルホン酸系界面活性剤(スルホン酸A~D)の合計質量に対するLAS-12の含有量(質量%)を表し、「LAS-13(wt%)」欄は、スルホン酸系界面活性剤(スルホン酸A~D)の合計質量に対するLAS-13の含有量(質量%)を表す。
表1および2中、「A/B」の表記は、洗浄組成物中の、HEDPOの含有量に対するクエン酸の含有量の質量比を表す。
表1および2中、「A/C」の表記は、洗浄組成物中の、スルホン酸系界面活性剤の含有質量の合計量に対するクエン酸の含有量の質量比を表す。
実施例105と実施例201~204との比較から、炭素数10のアルキル基を含むABS1と、炭素数11のアルキル基を含むABS2と、炭素数12のアルキル基を含むABS3と、炭素数13のアルキル基を含むABS4とを含むと、残渣の除去性、および、銅の防食性がより優れることが確認された。
実施例101~116の結果から、1-ヒドロキシエタン-1,1-ジホスホン酸の含有量に対するクエン酸の含有量の質量比が30~100であると、残渣の除去性、および、銅の防食性の少なくともいずれか一方がより優れることが確認された。
実施例101~116の結果から、1-ヒドロキシエタン-1,1-ジホスホン酸の含有量に対するクエン酸の含有量の質量比が40~80であると、残渣の除去性、および、銅の防食性の少なくともいずれか一方がより優れることが確認された。
実施例101~116の結果から、1-ヒドロキシエタン-1,1-ジホスホン酸の含有量に対するクエン酸の含有量の質量比が50~60であると、残渣の除去性、および、銅の防食性の少なくともいずれか一方がより優れることが確認された。
実施例101~116の結果から、スルホン酸系界面活性剤の含有量に対するクエン酸の含有量の質量比が200~600であると、残渣の除去性、および、銅の防食性の少なくともいずれか一方がより優れることが確認された。
実施例101~116の結果から、スルホン酸系界面活性剤の含有量に対するクエン酸の含有量の質量比が300~500であると、残渣の除去性、および、銅の防食性の少なくともいずれか一方がより優れることが確認された。
実施例101~116の結果から、スルホン酸系界面活性剤の含有量に対するクエン酸の含有量の質量比が410~440であると、残渣の除去性、および、銅の防食性の少なくともいずれか一方がより優れることが確認された。
実施例105および117~121の結果から、洗浄組成物全質量に対するクエン酸の含有量が、0.1~35.0質量%であると、残渣の除去性、および、銅の防食性の少なくともいずれか一方がより優れることが確認された。
実施例105および117~121の結果から、洗浄組成物全質量に対するクエン酸の含有量が、1.0~35.0質量%であると、残渣の除去性、および、銅の防食性の少なくともいずれか一方がより優れることが確認された。
実施例105および117~121の結果から、洗浄組成物全質量に対するクエン酸の含有量が、20.0~35.0質量%であると、残渣の除去性、および、銅の防食性の少なくともいずれか一方がより優れることが確認された。
Claims (17)
- クエン酸と、
1-ヒドロキシエタン-1,1-ジホスホン酸と、
スルホン酸系界面活性剤と、
水と、を含み、
前記1-ヒドロキシエタン-1,1-ジホスホン酸の含有量に対する前記クエン酸の含有量の質量比が20~150であり、
前記スルホン酸系界面活性剤の含有量に対する前記クエン酸の含有量の質量比が70~1500であり、
pHが0.10~4.00である、洗浄組成物。 - 前記スルホン酸系界面活性剤が、アルキルベンゼンスルホン酸系界面活性剤を含む、請求項1に記載の洗浄組成物。
- 前記アルキルベンゼンスルホン酸系界面活性剤が、アルキル基の炭素数が8以上であるアルキルベンゼンスルホン酸系界面活性剤を含む、請求項2に記載の洗浄組成物。
- 前記アルキルベンゼンスルホン酸系界面活性剤が、アルキル基の炭素数が10~13であるアルキルベンゼンスルホン酸系界面活性剤を含む、請求項2または3に記載の洗浄組成物。
- 前記スルホン酸系界面活性剤が、
炭素数10のアルキル基を含むアルキルベンゼンスルホン酸系界面活性剤1と、
炭素数11のアルキル基を含むアルキルベンゼンスルホン酸系界面活性剤2と、
炭素数12のアルキル基を含むアルキルベンゼンスルホン酸系界面活性剤3と、
炭素数13のアルキル基を含むアルキルベンゼンスルホン酸系界面活性剤4と、を含む、請求項1~4のいずれか1項に記載の洗浄組成物。 - 前記アルキルベンゼンスルホン酸系界面活性剤1~4の合計質量に対する前記アルキルベンゼンスルホン酸系界面活性剤2の含有量が、20~50質量%である、請求項5に記載の洗浄組成物。
- 前記1-ヒドロキシエタン-1,1-ジホスホン酸の含有量に対する前記クエン酸の含有量の質量比が30~100である、請求項1~6のいずれか1項に記載の洗浄組成物。
- 前記1-ヒドロキシエタン-1,1-ジホスホン酸の含有量に対する前記クエン酸の含有量の質量比が40~80である、請求項1~7のいずれか1項に記載の洗浄組成物。
- 前記1-ヒドロキシエタン-1,1-ジホスホン酸の含有量に対する前記クエン酸の含有量の質量比が50~60である、請求項1~8のいずれか1項に記載の洗浄組成物。
- 前記スルホン酸系界面活性剤の含有量に対する前記クエン酸の含有量の質量比が200~600である、請求項1~9のいずれか1項に記載の洗浄組成物。
- 前記スルホン酸系界面活性剤の含有量に対する前記クエン酸の含有量の質量比が300~500である、請求項1~10のいずれか1項に記載の洗浄組成物。
- 前記スルホン酸系界面活性剤の含有量に対する前記クエン酸の含有量の質量比が410~440である、請求項1~11のいずれか1項に記載の洗浄組成物。
- 洗浄組成物全質量に対する前記クエン酸の含有量が、0.1~35.0質量%である、請求項1~12のいずれか1項に記載の洗浄組成物。
- 洗浄組成物全質量に対する前記クエン酸の含有量が、1.0~35.0質量%である、請求項1~13のいずれか1項に記載の洗浄組成物。
- 洗浄組成物全質量に対する前記クエン酸の含有量が、20.0~35.0質量%である、請求項1~14のいずれか1項に記載の洗浄組成物。
- 請求項1~15のいずれか1項に記載の洗浄組成物を用いて半導体基板を洗浄する、半導体基板の洗浄方法。
- 請求項16に記載の半導体基板の洗浄方法を含む、半導体素子の製造方法。
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US20240067901A1 (en) | 2024-02-29 |
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TW202248407A (zh) | 2022-12-16 |
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