WO2020040003A1 - Chemical solution and chemical solution container - Google Patents
Chemical solution and chemical solution container Download PDFInfo
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- WO2020040003A1 WO2020040003A1 PCT/JP2019/031855 JP2019031855W WO2020040003A1 WO 2020040003 A1 WO2020040003 A1 WO 2020040003A1 JP 2019031855 W JP2019031855 W JP 2019031855W WO 2020040003 A1 WO2020040003 A1 WO 2020040003A1
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- mass
- chemical solution
- oxide particles
- metal component
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- 239000000126 substance Substances 0.000 title claims abstract description 167
- 229910052751 metal Inorganic materials 0.000 claims abstract description 115
- 239000002184 metal Substances 0.000 claims abstract description 115
- -1 silver ions Chemical class 0.000 claims abstract description 86
- 229910052709 silver Inorganic materials 0.000 claims abstract description 42
- 239000004332 silver Substances 0.000 claims abstract description 41
- 239000003960 organic solvent Substances 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims description 145
- 238000000034 method Methods 0.000 claims description 74
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 46
- 239000007788 liquid Substances 0.000 claims description 41
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 35
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 35
- 239000003814 drug Substances 0.000 claims description 34
- 229940079593 drug Drugs 0.000 claims description 31
- 239000010936 titanium Substances 0.000 claims description 28
- 229910052719 titanium Inorganic materials 0.000 claims description 25
- 229910001923 silver oxide Inorganic materials 0.000 claims description 23
- 239000012535 impurity Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
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- 230000003749 cleanliness Effects 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane of uncertain configuration Natural products CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011045 prefiltration Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003378 silver Chemical group 0.000 description 1
- DTPQZKZONQKKSU-UHFFFAOYSA-N silver azanide silver Chemical compound [NH2-].[Ag].[Ag].[Ag+] DTPQZKZONQKKSU-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/06—Silver salts
- G03F7/063—Additives or means to improve the lithographic properties; Processing solutions characterised by such additives; Treatment after development or transfer, e.g. finishing, washing; Correction or deletion fluids
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
-
- 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
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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 drug solution and a drug solution container.
- a semiconductor device by a wiring forming process including photolithography, a pre-wet solution, a resist solution (composition for forming a resist film), a developing solution, a rinsing solution, a stripping solution, and chemical mechanical polishing (CMP).
- a chemical solution containing water and / or an organic solvent is used as a slurry, a cleaning solution after CMP, or a diluent thereof.
- miniaturization of patterns has been progressing due to the progress of photolithography technology.
- pattern miniaturization pattern formation using an ultraviolet light, a KrF excimer laser, an ArF excimer laser, EUV (extreme ultraviolet light), or the like as an exposure light source has been attempted.
- EUV extreme ultraviolet light
- Patent Literature 1 discloses, as a conventional chemical solution used for pattern formation, “a method for producing an organic treatment solution for patterning a chemically amplified resist film capable of reducing generation of particles in a pattern formation technique (paragraph [0010]). ) "Is disclosed.
- An object of the present invention is to provide a chemical solution that is less likely to cause metal residue defects when brought into contact with a silicon substrate.
- Another object of the present invention is to provide a drug solution container.
- the present inventors have conducted intensive studies to solve the above-described problems, and as a result, have found that the above-described problems can be solved by the following configuration.
- a chemical solution containing an organic solvent and a metal component contains silver ions, A chemical solution having a silver ion content of 0.0010 to 1.0 mass ppt, based on the total mass of the chemical solution.
- the chemical according to (1) wherein the content of the metal component is 10.0 to 500 mass ppt based on the total mass of the chemical.
- the metal component contains silver oxide particles, The chemical solution according to (2), wherein the mass ratio 1 of the content of silver oxide particles to the content of silver ions is from 0.000000010 to 0.1.
- the metal component contains titanium oxide particles and titanium ions
- Formula (A) Mass ratio 2> Mass ratio 1 (6)
- the metal component contains copper oxide particles and copper ions, The chemical solution according to any one of (3) to (9), wherein the mass ratio of the content of copper oxide particles to the content of copper ions and the mass ratio satisfy the relationship of the following formula (B).
- the metal component contains iron oxide particles and iron ions, The chemical solution according to any one of (3) to (9), wherein the mass ratio of the content of the iron oxide particles to the content of iron ions and the mass ratio satisfy the relationship of the following formula (C).
- the metal component contains a platinum ion, The chemical solution according to any one of (1) to (11), wherein the content of platinum ions is 0.000010 to 1.0 mass ppt based on the total mass of the chemical solution. (13) The metal component contains gold ions, The chemical solution according to any one of (1) to (12), wherein the content of the gold ion is 0.00010 to 1.0 mass ppt based on the total mass of the chemical solution. (14) It further contains organic impurities, The chemical solution according to any one of (1) to (13), wherein the content of the organic impurities is 1,000 to 100,000 mass ppt based on the total mass of the chemical solution.
- the drug solution according to any one of (1) to (14), wherein the content of water with respect to the total weight of the drug solution is 500 mass ppb or less.
- the organic solvent is propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, propylene carbonate, isopropanol, 4-methyl-2-pentanol, butyl acetate, propylene glycol monoethyl ether, propylene glycol monopropyl Ether, methyl methoxypropionate, cyclopentanone, ⁇ -butyrolactone, diisoamyl ether, isoamyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cycloheptanone , 2-heptanone, butyl butyl
- the chemical liquid which a metal residue defect does not generate easily can be provided.
- a drug solution container can be provided.
- a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
- ppm means “parts-per-million (10 ⁇ 6 )”
- ppb means “parts-per-billion (10 ⁇ 9 )”
- ppt means “Parts-per-trillion (10 ⁇ 12 )” means “parts-per-quadrillion (10 ⁇ 15 )”.
- the notation that does not indicate substitution or unsubstitution means a group containing a substituent together with a group having no substituent within a range not impairing the effect of the present invention.
- the “hydrocarbon group” includes not only a hydrocarbon group having no substituent (unsubstituted hydrocarbon group) but also a hydrocarbon group having a substituent (substituted hydrocarbon group). This is the same for each compound.
- “radiation” in the present invention means, for example, far ultraviolet rays, extreme ultraviolet (EUV), X-rays, or electron beams. In the present invention, light means actinic rays or radiation.
- the term “exposure” in the present invention includes not only exposure with far ultraviolet rays, X-rays or EUV, but also drawing with particle beams such as electron beams or ion beams.
- the present inventors presume the mechanism as follows. In addition, the following mechanism is speculation, and even when the effect of the present invention is obtained by a different mechanism, it is included in the scope of the present invention.
- the present inventors have found that when a chemical solution contains silver ions, the likelihood of metal residue defects (residues derived from metal components) on a silicon substrate varies depending on the content of silver ions. More specifically, when the amount of silver ions exceeds a predetermined value, many silver ions are present, so that the silver ions are reduced on the silicon substrate, and a large amount of silver particles adhere to the silicon substrate, and It is considered that residue defects have occurred.
- the chemical solution of the present invention is a chemical solution containing an organic solvent and a metal component, wherein the metal component contains silver ions, and the content of silver ions is 0.0010 to 1.0. 0 mass ppt.
- the components contained in the chemical solution of the present invention will be described in detail.
- the chemical solution of the present invention contains an organic solvent.
- an organic solvent is intended to mean a liquid organic compound contained at a content exceeding 10,000 mass ppm per component with respect to the total mass of the chemical solution. That is, in this specification, a liquid organic compound contained in an amount exceeding 10,000 ppm by mass with respect to the total mass of the chemical solution corresponds to an organic solvent.
- the term “liquid” means a liquid at 25 ° C. and atmospheric pressure.
- the content of the organic solvent in the chemical solution is not particularly limited, but is preferably 98.0% by mass or more, more preferably more than 99.0% by mass, and more preferably 99.90% by mass or more based on the total mass of the chemical solution. Preferably, it is more than 99.95% by mass. The upper limit is less than 100% by mass.
- One type of organic solvent may be used alone, or two or more types may be used. When two or more organic solvents are used, the total content is preferably within the above range.
- the type of the organic solvent is not particularly limited, and a known organic solvent can be used.
- the organic solvent include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), and monoketone compound optionally having a ring. (Preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate, dialkyl sulfoxide, cyclic sulfone, dialkyl ether, monohydric alcohol, glycol, alkyl acetate, and N-alkylpyrrolidone. .
- organic solvent examples include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), propylene carbonate (PC), isopropanol (IPA), and 4-methyl-2.
- PGMEA propylene glycol monomethyl ether acetate
- PGME propylene glycol monomethyl ether
- CHN propylene glycol monomethyl ether
- EL ethyl lactate
- PC propylene carbonate
- IPA isopropanol
- MIBC -Pentanol
- nBA butyl acetate
- propylene glycol monoethyl ether propylene glycol monopropyl ether, methyl methoxypropionate, cyclopentanone, ⁇ -butyrolactone, diisoamyl ether, isoamyl acetate, dimethyl sulfoxide, N- Methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cycloheptanone, Heptanone, butyl butyrate, isobutyl isobutyrate, isoamyl ether, and one or more selected from the group consisting of undecane is preferred.
- Examples of using two or more organic solvents include a combination of PGMEA and PGME, and a combination of PGMEA and PC.
- the kind and content of the organic solvent in the chemical solution can be measured using a gas chromatograph mass spectrometer.
- the chemical solution contains a metal component.
- the metal component is composed of metal-containing particles and metal ions.
- the content of the metal component indicates the total content of the metal-containing particles and metal ions.
- the metal-containing particles only need to include metal atoms, and examples thereof include metal oxide particles, metal nitride particles, and metal particles.
- the metal particles mean particles composed of only metal.
- the metal component contained in the chemical solution contains silver ions.
- the content of silver ions is 0.0010 to 1.0 mass ppt with respect to the total mass of the chemical solution, and 0.0020 to 0.90 mass ppt is low in that metal residue defects are less likely to occur on the silicon substrate.
- 0.05 to 0.90 mass ppt is more preferable, and 0.10 to 0.90 mass ppt is more preferable.
- the metal component contained in the chemical solution may contain silver oxide particles.
- the mass ratio of the content of silver oxide particles to the content of silver ions (1) is not particularly limited. 000000010 to 1.5 in many cases. Above all, the mass ratio 1 is preferably from 0.000000010 to 0.1, and more preferably from 0.000001 to 0, in that metal residue defects or composite residue defects described later are less likely to occur on a silicon substrate or a silicon oxide film. 0.01 and more preferably 0.00001 to 0.005.
- the content of the silver oxide particles is not particularly limited, and is often 0.00001 to 10% by mass based on the content of the silver component in the metal component. Among them, the content of silver oxide particles is preferably from 0.00010 to 5.0% by mass, more preferably from 0.010 to 1% by mass, based on the content of the silver component in the metal component, in that the effect of the present invention is more excellent. 0.0% by mass is more preferred.
- the silver component is a component containing a silver atom and is composed of silver-containing particles and silver ions. For example, when the content of the silver component is referred to, it indicates the total content of the silver-containing particles and silver ions.
- the silver-containing particles only need to contain silver atoms, and examples thereof include silver oxide particles, silver nitride particles, and silver particles.
- the silver particles mean particles made of metallic silver.
- the metal component contained in the chemical solution may contain components other than the silver component.
- the metal component contained in the chemical solution may contain a titanium component.
- the titanium component is a component containing a titanium atom, and is composed of titanium-containing particles and titanium ions. For example, when referring to the content of the titanium component, it indicates the total content of the titanium-containing particles and titanium ions.
- the titanium-containing particles only need to contain titanium atoms, and examples thereof include titanium oxide particles, titanium nitride particles, and titanium particles.
- the titanium particles mean particles made of titanium metal.
- the metal component contained in the chemical solution may contain titanium oxide particles and titanium ions.
- the mass ratio 2 of the content of the titanium oxide particles to the content of the titanium ions is not particularly limited, but the mass ratio 1 described above and the following formula (A) It is preferable to satisfy the relationship.
- the ratio of the content of the titanium oxide particles to the content of the silver oxide particles is not particularly limited, and is often 10 1 to 10 10 . Above all, the ratio is preferably 10 2 to 10 10, and more preferably 10 3 to 10 10 , in that metal residue defects or composite residue defects described later are less likely to occur on the silicon substrate or the silicon oxide film.
- the number of the titanium oxide particles is not particularly limited, 10 0 to 10 11 pieces of often. Among them, the number of titanium oxide particles is preferably 10 2 to 10 10, and more preferably 10 3 to 10 10 , in that metal residue defects or composite residue defects described later are less likely to occur on the silicon substrate or the silicon oxide film. Are more preferred.
- the content of the titanium oxide particles is not particularly limited, and is often 1 to 99% by mass based on the content of the titanium component in the metal component. Among them, on the silicon substrate or on the silicon oxide film, metal residue defects or composite residue defects described below are less likely to occur, the content of the titanium oxide particles is relative to the content of the titanium component in the metal component. It is preferably from 5% by mass to less than 98% by mass, more preferably from 10 to 90% by mass.
- the proportion of the titanium oxide particles having a particle size of 0.5 to 17 nm is not particularly limited, and is often 30 to 99% by mass.
- the ratio of particles having a particle size of 0.5 to 17 nm among titanium oxide particles is 40% because metal residue defects or composite residue defects described later are less likely to be formed on a silicon substrate or a silicon oxide film. It is preferably at least 70% by mass and less than 99% by mass, more preferably 70 to 98% by mass.
- the metal component contained in the chemical solution may contain platinum ions.
- the content of platinum ions is not particularly limited, and is often 0.000001 to 1.5 mass ppt based on the total mass of the chemical solution. Above all, the content of platinum ions is preferably 0.000010 to 1.0 mass ppt, based on the total mass of the chemical solution, in that metal residue defects or composite residue defects described below are less likely to occur on the silicon substrate. 0.00010 to 0.50 mass ppt is more preferable, and more preferably 0.001% by mass or more and less than 0.20 mass ppt.
- the metal component contained in the chemical solution may contain gold ions. The content of the gold ion is not particularly limited, and is often 0.000001 to 1.5 mass ppt based on the total mass of the chemical solution.
- the content of gold ions is preferably 0.000010 to 1.0 mass ppt, based on the total mass of the chemical solution, in that metal residue defects or composite residue defects described below are less likely to occur on the silicon substrate.
- 0.00010 to 1.0 mass ppt is more preferable, and 0.001 mass% or more and less than 0.10 mass ppt is more preferable.
- the metal component contained in the chemical solution may contain components of other metal atoms than those described above.
- Other metal atoms include, for example, Na (sodium), K (potassium), Ca (calcium), Fe (iron), Cu (copper), Mg (magnesium), Mn (manganese), Li (lithium), Al (Aluminum), Cr (chromium), Ni (nickel), and Zn (zirconium).
- the metal component contained in the chemical solution may contain copper oxide particles and copper ions.
- the mass ratio 3 of the content of the copper oxide particles to the content of the copper ions is not particularly limited, but the mass ratio 1 described above and the following formula (B) It is preferable to satisfy the relationship.
- the metal component contained in the chemical solution may contain iron oxide particles and iron ions.
- the mass ratio 4 of the content of iron oxide particles to the content of iron ions (content of iron oxide particles / content of iron ions) is not particularly limited, but the mass ratio 1 described above and the following formula (C) are used. It is preferable to satisfy the relationship.
- the metal component may be a metal component inevitably included in each component (raw material) included in the chemical solution, or may be a metal component inevitably included in manufacturing, storing, and / or transferring the chemical solution, It may be added intentionally.
- the content of the metal component is not particularly limited, the metal residue defect or the composite residue defect described later is less likely to be formed on the silicon substrate or the silicon oxide film, and the content is 1 to 500,000 mass% based on the total mass of the chemical solution. ppt is preferable, and 5 to 1000 mass ppt is more preferable.
- the types and contents of metal ions and metal-containing particles in a chemical solution can be measured by an SP-ICP-MS method (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry).
- the SP-ICP-MS method uses an apparatus similar to a normal ICP-MS method (inductively coupled plasma mass spectrometry), and differs only in data analysis. Data analysis of the SP-ICP-MS method can be performed by commercially available software.
- the content of a metal component to be measured is measured regardless of its existing form. Therefore, the total mass of the metal-containing particles to be measured and the metal ions is determined as the content of the metal component.
- the content of metal-containing particles can be measured. Therefore, by subtracting the content of the metal-containing particles from the content of the metal component in the sample, the content of the metal ion in the sample can be calculated.
- Agilent 8800 triple quadrupole ICP-MS inductively coupled plasma mass spectrometry, option # 200 for semiconductor analysis, option # 200
- Agilent Technologies, Inc. is described in Examples. Can be measured by the following method.
- Agilent 8900 manufactured by Agilent Technologies can be used as an apparatus other than the above.
- the method described in paragraphs 0015 to 0067 of JP-A-2009-188333 (hereinafter, also referred to as “specific method”) is used.
- the number of particles of 0.5 to 10 nm remaining on the substrate is counted by a specific method, and the converted value of the 20 nm particles from SNP-ICP-MS is used for the count.
- the conversion value differs for each metal, this conversion is performed for each metal.
- the specific method of conversion is as follows.
- the converted value Becomes 10. That is, when the number of 1 nm titanium oxide particles confirmed by the specific method is 100, the number is calculated as 1000 (100 ⁇ 10) in the chemical based on 10 times the converted value.
- the number of particles having a size of 10 nm or less in the present invention is estimated by this conversion method regardless of the type of metal.
- the chemical may contain organic impurities.
- the content of the organic impurities in the chemical solution is not particularly limited, but is preferably from 1,000 to 100,000 mass ppt based on the total mass of the chemical solution from the viewpoint that stain-like residue defects described later are less likely to be formed on the silicon substrate.
- the organic impurity is an organic compound different from the organic solvent, and means an organic compound contained at a content of 10000 ppm by mass or less based on the total mass of the organic solvent. That is, in the present specification, an organic compound contained at a content of 10,000 mass ppm or less based on the total mass of the organic solvent corresponds to an organic impurity and does not correspond to an organic solvent.
- Organic impurities are often mixed with or added to a chemical solution during the process of refining a substance to be purified to obtain a chemical solution.
- organic impurities include a plasticizer, an antioxidant, and a compound derived from these (typically, a decomposition product).
- the drug solution may contain water.
- Water is not included in the organic impurities.
- the water is not particularly limited, and for example, distilled water, ion-exchanged water, pure water, and the like can be used.
- Water may be added to the chemical solution, or may be unintentionally mixed into the chemical solution in the process of manufacturing the chemical solution. Examples of the case of being unintentionally mixed in the manufacturing process of the chemical solution include, for example, the case where water is contained in a raw material (for example, an organic solvent) used for manufacturing the chemical solution, and the mixing in the manufacturing process of the chemical solution ( For example, contamination) is not limited to the above.
- the content of water in the chemical is not particularly limited, but is preferably 2.0% by mass or less, more preferably 500% by mass or less, based on the total mass of the chemical.
- the lower limit is not particularly limited, but may be 0% by mass.
- the water content in the chemical solution means the water content measured using an apparatus based on the Karl Fischer moisture measurement method.
- the chemical solution of the present invention is preferably used for manufacturing a semiconductor device. Especially, it is preferable to manufacture a semiconductor chip using the chemical solution of the present invention. Specifically, in a semiconductor device manufacturing process including a lithography process, an etching process, an ion implantation process, and a peeling process, an organic material is processed after each process or before moving to the next process. Specifically, it is suitably used as a pre-wet liquid, a developing liquid, a rinsing liquid, a polishing liquid or the like. In addition, the chemical solution may be used as a diluting solution of the resin contained in the resist film forming composition (in other words, a solvent).
- the above-mentioned chemical solution can be used for other uses other than the production of semiconductor devices, and can also be used as a developer and a rinse for polyimide, a resist for sensors, a resist for lenses, and the like.
- the above chemical solution can be used as a solvent for medical use or cleaning use.
- it can be suitably used for cleaning pipes, containers, and substrates (for example, wafers and glass).
- a cleaning liquid a pipe cleaning liquid and a container cleaning liquid, etc.
- a liquid such as the above-mentioned pre-wet liquid.
- the chemical solution is suitably used for a pre-wet solution, a developing solution, a rinsing solution, a polishing solution, and a composition for forming a resist film.
- a pre-wet liquid when applied to a pre-wet liquid, a developing liquid and a rinsing liquid, more excellent effects are exhibited.
- a developing liquid and a rinsing liquid when the exposure light source is EUV, a more excellent effect is exhibited.
- a pipe cleaning liquid used for pipes used for transferring these liquids more excellent effects are exhibited.
- the method for producing the chemical solution is not particularly limited, and a known production method can be used. Above all, in that a drug solution exhibiting a better effect of the present invention can be obtained, the method for producing a drug solution has a filtration step of filtering a substance to be purified containing an organic solvent using a filter to obtain a drug solution. Is preferred.
- the material to be purified used in the filtration step may be procured by purchasing or the like, or may be obtained by reacting the raw materials. It is preferable that the material to be purified has a low impurity content. Examples of such a commercially available product to be purified include a commercially available product called “high-purity grade product”.
- the method of obtaining the object to be purified typically, the object to be purified containing an organic solvent
- a known method can be used.
- a method of reacting acetic acid and n-butanol in the presence of sulfuric acid to obtain butyl acetate reacting ethylene, oxygen, and water in the presence of Al (C 2 H 5 ) 3 Reacting cis-4-methyl-2-pentene in the presence of Ipc2BH (Diisopinocampheylborane) to obtain 4-methyl-2-pentanol; propylene oxide, methanol and acetic acid Is reacted in the presence of sulfuric acid to obtain PGMEA (propylene glycol 1-monomethyl ether 2-acetate); acetone and hydrogen are reacted in the presence of copper oxide-zinc oxide-aluminum oxide to give IPA (isopropyl). alcohol) by reacting lactic acid and ethanol to obtain lactic acid. And the like; a method of obtaining a chill.
- the method for producing a drug solution of the present invention preferably includes a filtration step of filtering the above-mentioned substance to be purified using a filter to obtain a drug solution.
- the method of filtering the object to be purified using a filter is not particularly limited, and the object to be purified is passed through a filter unit having a housing and a filter cartridge housed in the housing with or without pressurization ( Is preferable.
- the pore size of the filter is not particularly limited, and a filter having a pore size usually used for filtering a substance to be purified can be used.
- the pore diameter of the filter is preferably 200 nm or less, more preferably 20 nm or less, still more preferably 10 nm or less, and more preferably 5 nm or less, in that the number of particles (metal particles and the like) contained in the drug solution can be easily controlled in a desired range. Is particularly preferred.
- the lower limit is not particularly limited, but is generally preferably 1 nm or more from the viewpoint of productivity.
- the pore diameter of a filter means the pore diameter determined by the bubble point of isopropanol (IPA).
- the pore diameter of the filter be 5.0 nm or less, since the number of particles contained in the drug solution can be more easily controlled.
- a filter having a pore size of 5.0 nm or less is also referred to as a “micropore size filter”.
- the micropore size filter may be used alone, or may be used with a filter having another pore size. Among them, it is preferable to use a filter having a larger pore diameter from the viewpoint of better productivity. That is, when two or more filters are used, it is preferable that at least one filter has a pore diameter of 5.0 nm or less.
- the object to be purified which has been filtered through a filter having a larger pore diameter in advance, is passed through a micropore size filter, clogging of the micropore size filter can be prevented. That is, when one filter is used, the pore diameter of the filter is preferably 5.0 nm or less, and when two or more filters are used, the pore diameter of the filter having the smallest pore diameter is 5.0 nm. The following is preferred.
- the form in which two or more types of filters having different pore diameters are sequentially used is not particularly limited, and examples thereof include a method of sequentially arranging the above-described filter units along a pipe through which a substance to be purified is transferred.
- a larger pressure may be applied to a filter having a smaller pore size as compared with a filter having a larger pore size.
- a pressure regulating valve, a damper, etc. are arranged between the filters to make the pressure applied to the filter having a small pore diameter constant, or a filter unit containing the same filter is placed along the pipeline. It is preferable to increase the filtration area by arranging them in parallel. This makes it possible to more stably control the number of particles in the chemical solution.
- the material of the filter is not particularly limited, and known materials for the filter can be used. Specifically, when it is a resin, polyamide such as nylon (for example, 6-nylon and 6,6-nylon); polyolefin such as polyethylene and polypropylene; polystyrene; polyimide; polyamideimide; Polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylene propene copolymer, ethylene / tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride Fluorocarbon; polyvinyl alcohol; polyester; cellulose; cellulose acetate and the like.
- polyamide such as nylon (for example, 6-nylon and 6,6-nylon)
- polyolefin such as polyethylene and polypropylene
- polystyrene polyimide
- polyamideimide poly
- nylon especially, 6,6-nylon is preferred
- polyolefin especially, polyethylene is preferred
- polyolefin are preferred in that they have better solvent resistance and the resulting chemical has more excellent defect suppression performance.
- At least one selected from the group consisting of (meth) acrylate and polyfluorocarbon (among others, polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkane (PFA) is preferable) is preferable.
- PTFE polytetrafluoroethylene
- PFA perfluoroalkoxyalkane
- a polymer eg, nylon grafted UPE obtained by graft copolymerizing a polyamide (eg, nylon-6 or nylon-6,6, etc.) with a polyolefin (eg, UPE (ultra high molecular weight polyethylene) described below) is used as a filter.
- a polyamide eg, nylon-6 or nylon-6,6, etc.
- a polyolefin eg, UPE (ultra high molecular weight polyethylene) described below
- the filter may be a surface-treated filter.
- the method for surface treatment is not particularly limited, and a known method can be used. Examples of the surface treatment method include chemical modification treatment, plasma treatment, hydrophobic treatment, coating, gas treatment, and sintering.
- Plasma treatment is preferable because the surface of the filter becomes hydrophilic.
- the water contact angle on the surface of the filter that has been hydrophilized by plasma treatment is not particularly limited, but the static contact angle at 25 ° C. measured by a contact angle meter is preferably 60 ° or less, more preferably 50 ° or less, 30 ° or less is more preferable.
- a method of introducing an ion exchange group into a filter is preferable. That is, a filter having an ion exchange group is preferable as the filter.
- the ion exchange group include a cation exchange group and an anion exchange group.
- the cation exchange group include a sulfonic acid group, a carboxy group, and a phosphate group, and examples of the anion exchange group include a quaternary ammonium group.
- the method for introducing the ion-exchange group into the filter is not particularly limited, and examples thereof include a method in which a compound containing an ion-exchange group and a polymerizable group is allowed to react with the filter and typically grafted.
- the method of introducing the ion exchange group is not particularly limited, but the filter is irradiated with ionizing radiation ( ⁇ -ray, ⁇ -ray, ⁇ -ray, X-ray, electron beam, etc.) to generate an active portion (radical).
- ionizing radiation ⁇ -ray, ⁇ -ray, ⁇ -ray, X-ray, electron beam, etc.
- the filter after the irradiation is immersed in the monomer-containing solution, and the monomer is graft-polymerized on the filter.
- a polymer obtained by polymerizing this monomer is grafted on the filter.
- the produced polymer can be brought into contact with a compound containing an anion exchange group or a cation exchange group to introduce an ion exchange group into the polymer.
- the filter may have a structure in which a woven or nonwoven fabric having an ion exchange group formed by a radiation graft polymerization method is combined with a conventional glass wool, woven or nonwoven fabric filter material.
- the material constituting the filter having an ion exchange group is not particularly limited, and examples thereof include a polyfluorocarbon and a material in which an ion exchange group is introduced into polyolefin, and a material in which an ion exchange group is introduced into polyfluorocarbon is more preferable.
- the pore diameter of the filter having an ion exchange group is not particularly limited, it is preferably 1 to 30 nm, more preferably 5 to 20 nm.
- the filter having an ion-exchange group may also serve as the filter having the smallest pore diameter described above, or may be used separately from the filter having the smallest pore diameter.
- the filtration step uses a filter having an ion exchange group and a filter having no ion exchange group and having a minimum pore diameter. Is preferred.
- the material of the filter having the smallest pore diameter already described is not particularly limited, but from the viewpoint of solvent resistance and the like, generally, polyfluorocarbon, and at least one selected from the group consisting of polyolefins are preferable. More preferred.
- the filter used in the filtration step two or more types of filters having different materials may be used.
- polyolefins, polyfluorocarbons, polyamides, and filters made of materials having ion exchange groups introduced therein may be used. Two or more kinds selected from the group may be used.
- the pore structure of the filter is not particularly limited, and may be appropriately selected according to the components in the object to be purified.
- the pore structure of a filter means a pore size distribution, a positional distribution of pores in a filter, and a shape of pores, and is typically controlled by a filter manufacturing method. It is possible.
- a porous film can be obtained by sintering a powder of a resin or the like, and a fiber film can be obtained by forming by a method such as electrospinning, electroblowing, and meltblowing. These have different pore structures.
- a “porous membrane” refers to a membrane that retains components in an object to be purified, such as gels, particles, colloids, cells, and poly-oligomers, but a component that is substantially smaller than the pores passes through the pores.
- the retention of components in the object to be purified by the porous membrane may depend on operating conditions, such as surface velocity, use of surfactant, pH, and combinations thereof, and the pore size of the porous membrane, It may depend on the structure and the size of the particles to be removed, and the structure (hard particles or gels, etc.).
- non-sieving membranes include, but are not limited to, nylon-6 membranes and nylon membranes such as nylon-6,6 membranes.
- non-sieving retention mechanism refers to retention caused by mechanisms such as filter pressure drop or interference, diffusion, and adsorption that are not related to pore size.
- Non-sieve retention includes retention mechanisms, such as obstruction, diffusion, and adsorption, that remove particles to be removed from the object to be purified, regardless of the filter pressure drop or filter pore size.
- the adsorption of particles to the filter surface can be mediated, for example, by intermolecular van der Waals forces and electrostatic forces.
- An interfering effect occurs when particles traveling in a non-sieving membrane layer having a tortuous path are not turned fast enough to avoid contact with the non-sieving membrane.
- Particle transport by diffusion results primarily from random or Brownian motion of small particles, which creates a certain probability that the particles will collide with the filter media. If there is no repulsion between the particles and the filter, the non-sieve retention mechanism can be active.
- UPE filters are typically sieved membranes.
- a sieve membrane means a membrane that mainly captures particles via a sieve holding mechanism, or a membrane that is optimized for capturing particles via a sieve holding mechanism.
- Typical examples of sieving membranes include, but are not limited to, polytetrafluoroethylene (PTFE) membranes and UPE membranes.
- PTFE polytetrafluoroethylene
- the “sieve holding mechanism” refers to holding the result due to the removal target particles being larger than the pore diameter of the porous membrane.
- the sieve retention is improved by forming a filter cake (agglomeration of the particles to be removed on the surface of the membrane). The filter cake effectively performs the function of a secondary filter.
- the material of the fiber membrane is not particularly limited as long as it is a polymer capable of forming the fiber membrane.
- the polymer include polyamide and the like.
- the polyamide include nylon 6, nylon 6,6, and the like.
- the polymer forming the fiber membrane may be poly (ether sulfone).
- the surface energy of the fibrous membrane is preferably higher than the polymer which is the material of the porous membrane on the secondary side.
- An example of such a combination is a case where the material of the fiber membrane is nylon and the porous membrane is polyethylene (UPE).
- the method for producing the fiber membrane is not particularly limited, and a known method can be used.
- Examples of the method for producing a fiber membrane include electrospinning, electroblowing, and meltblowing.
- the pore structure of the porous membrane is not particularly limited, and examples of the pore shape include a lace shape, a string shape, and a node shape.
- Can be The distribution of pore sizes in the porous membrane and the distribution of positions in the membrane are not particularly limited.
- the size distribution may be smaller and the distribution position in the film may be symmetric. Further, the size distribution may be larger and the distribution position in the film may be asymmetric (the above film is also referred to as “asymmetric porous film”).
- asymmetric porous membrane the size of the pores varies in the membrane, and typically the pore size increases from one surface of the membrane to the other surface of the membrane.
- the surface on the side with many pores having a large pore diameter is called “open side”, and the surface on the side with many pores with small pore diameter is also called “tight side”.
- the asymmetric porous membrane include a membrane in which the size of pores is minimized at a certain position within the thickness of the membrane (this is also referred to as an “hourglass shape”).
- the primary side is made to have a larger-sized pore using the asymmetric porous membrane, in other words, if the primary side is made to be the open side, a pre-filtration effect can be produced.
- the porous membrane may include thermoplastic polymers such as PESU (polyethersulfone), PFA (perfluoroalkoxyalkane, copolymer of ethylene tetrafluoride and perfluoroalkoxyalkane), polyamide, and polyolefin. , Polytetrafluoroethylene and the like. Among them, ultrahigh molecular weight polyethylene is preferable as the material of the porous membrane. Ultra-high molecular weight polyethylene means a thermoplastic polyethylene having an extremely long chain, and preferably has a molecular weight of 1,000,000 or more, typically 2,000,000 to 6,000,000.
- a filter used in the filtration step two or more types of filters having different pore structures may be used, or a filter of a porous membrane and a filter of a fiber membrane may be used in combination. Specific examples include a method using a nylon fiber membrane filter and a UPE porous membrane filter.
- the filter is sufficiently washed before use.
- impurities contained in the filter are likely to be brought into the chemical solution.
- At least one selected from the group consisting of a filter material, a pore diameter, and a pore structure passes the material to be purified through two or more types of different filters.
- a multi-stage filtration step The object to be purified may be passed through the same filter a plurality of times, or the object to be purified may be passed through a plurality of filters of the same type.
- a filter capable of selectively removing metal components such as “Purasol SN 200 nm” (metal component removal filter).
- the material of the liquid contacting portion of the purification device used in the filtration step is not particularly limited, but non-metallic materials (fluorinated resin And the like, and at least one selected from the group consisting of electrolytically polished metal materials (such as stainless steel) (hereinafter, these are collectively referred to as “corrosion-resistant materials”).
- non-metallic materials fluorinated resin And the like, and at least one selected from the group consisting of electrolytically polished metal materials (such as stainless steel) (hereinafter, these are collectively referred to as “corrosion-resistant materials”).
- the wetted part of a production tank is formed of a corrosion-resistant material, which means that the production tank itself is made of a corrosion-resistant material, or the inner wall of the production tank is coated with a corrosion-resistant material.
- the nonmetallic material is not particularly limited, and a known material can be used.
- the non-metallic material include polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, and fluorine-based resin (eg, ethylene tetrafluoride resin, ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer, -Propylene hexafluoride copolymer resin, ethylene tetrafluoride-ethylene copolymer resin, ethylene trifluoride-ethylene copolymer resin, vinylidene fluoride resin, ethylene trifluoride ethylene copolymer resin, and vinyl fluoride At least one selected from the group consisting of resins and the like, but is not limited thereto.
- the metal material is not particularly limited, and a known material can be used.
- the metal material include a metal material in which the total content of chromium and nickel is more than 25% by mass based on the total mass of the metal material, and among them, 30% by mass or more is more preferable.
- the upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is generally preferably 90% by mass or less.
- the metal material include stainless steel and a nickel-chromium alloy.
- the stainless steel is not particularly limited, and a known stainless steel can be used. Among them, alloys containing nickel at 8% by mass or more are preferable, and austenitic stainless steels containing nickel at 8% by mass or more are more preferable.
- austenitic stainless steel include SUS (Steel Use Stainless) 304 (Ni content 8% by mass, Cr content 18% by mass), SUS304L (Ni content 9% by mass, Cr content 18% by mass), SUS316 ( Ni content 10% by mass, Cr content 16% by mass) and SUS316L (Ni content 12% by mass, Cr content 16% by mass) and the like.
- the nickel-chromium alloy is not particularly limited, and a known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass is preferable. Examples of the nickel-chromium alloy include Hastelloy (trade name, the same applies hereinafter), Monel (trade name, the same applies hereinafter), and Inconel (trade name, the same applies hereinafter).
- Hastelloy C-276 (Ni content 63% by mass, Cr content 16% by mass), Hastelloy-C (Ni content 60% by mass, Cr content 17% by mass), and Hastelloy C-276 22 (Ni content 61% by mass, Cr content 22% by mass).
- the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt, and the like, if necessary, in addition to the above alloy.
- the method of electropolishing the 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 metal material has a higher chromium content in the passivation layer on the surface than a chromium content in the matrix due to electrolytic polishing. Therefore, it is presumed that the use of a refining device in which the liquid contact portion is formed from a metal material which has been electropolished, makes it difficult for metal-containing particles to flow out into the object to be purified.
- the metal material may be buffed.
- the buffing method is not particularly limited, and a known method can be used.
- the size of the abrasive grains used for the buffing finish is not particularly limited, but is preferably # 400 or less from the viewpoint that irregularities on the surface of the metal material tend to be smaller.
- the buff polishing is preferably performed before the electrolytic polishing.
- the method for producing a chemical solution may further include a step other than the filtration step.
- the steps other than the filtration step include, for example, a distillation step, a reaction step, and a charge removal step.
- the distillation step is a step of distilling an object to be purified containing an organic solvent to obtain a distilled object to be purified.
- the method for distilling the object to be purified is not particularly limited, and a known method can be used.
- a distillation column is arranged on the primary side of a purification device provided for a filtration step, and a distilled product to be purified is introduced into a production tank.
- the liquid contact portion of the distillation column is not particularly limited, but is preferably formed of the corrosion-resistant material described above.
- the reaction step is a step of reacting the raw materials to produce a purified product containing an organic solvent as a reactant.
- the method for producing the object to be purified is not particularly limited, and a known method can be used. Typically, there is a method in which a reaction tank is arranged on the primary side of a production tank (or a distillation column) of a purification device provided for a filtration step, and a reactant is introduced into the production tank (or a distillation column). At this time, the liquid contact portion of the production tank is not particularly limited, but is preferably formed of the corrosion-resistant material described above.
- the charge elimination step is a step of removing charges from the object to be purified to reduce the charged potential of the object to be purified.
- the static elimination method is not particularly limited, and a known static elimination method can be used.
- Examples of the charge removal method include a method of contacting the object to be purified with a conductive material.
- the contact time for contacting the object to be purified with the conductive material is preferably from 0.001 to 60 seconds, more preferably from 0.001 to 1 second, even more preferably from 0.01 to 0.1 second.
- the conductive material include stainless steel, gold, platinum, diamond, and glassy carbon.
- ⁇ Purification of the object to be purified is preferably performed in a clean room, in which the opening of the container, the cleaning of the container and the device, the storage of the solution, and the analysis are all performed.
- the clean room is preferably a clean room having a class 4 or higher cleanliness specified by International Standard ISO1464-1: 2015 specified by the International Organization for Standardization. Specifically, it is preferable to satisfy any one of ISO class 1, ISO class 2, ISO class 3, and ISO class 4, more preferably to satisfy ISO class 1 or ISO class 2, and to satisfy ISO class 1. Is more preferred.
- the storage temperature of the drug solution is not particularly limited, but the storage temperature is preferably 4 ° C. or higher from the viewpoint that impurities and the like contained in a small amount in the drug solution are less likely to be eluted and, as a result, a superior effect of the present invention can be obtained.
- the drug solution produced by the above purification method may be stored in a container and stored until use.
- a combination of such a container and a drug solution contained in the container is referred to as a drug solution container.
- the medicinal solution is taken out from the stored medicinal solution container and used.
- the container As a container for storing the chemical solution, it is preferable that the container has a high degree of cleanness and a small amount of impurities eluted for use in semiconductor device manufacturing.
- Specific examples of usable containers include, but are not limited to, “Clean Bottle” series manufactured by Aicello Chemical Co., Ltd. and “Pure Bottle” manufactured by Kodama Resin Kogyo.
- a multi-layer bottle having a six-layer structure made of six kinds of resins or a seven-layer structure made of six kinds of resins is used for the purpose of preventing impurities from being mixed into the chemical solution (contamination). Is also preferred. Examples of these containers include those described in JP-A-2015-123351.
- the liquid-contact part of this container may be a corrosion-resistant material (preferably, electropolished stainless steel or fluorine resin) or glass described above. It is preferable that 90% or more of the area of the liquid contact part is made of the above-mentioned material, and it is more preferable that all of the liquid contact part is made of the above-mentioned material from the viewpoint that the superior effects of the present invention can be obtained.
- the porosity of the liquid medicine container in the container is preferably 2 to 80% by volume, more preferably 2 to 50% by volume, and still more preferably 5 to 30% by volume. Note that the porosity is calculated according to equation (1).
- Formula (1): Porosity ⁇ 1 ⁇ (volume of drug solution in container / volume of container) ⁇ ⁇ 100
- the container volume is synonymous with the internal volume (capacity) of the container.
- the purified product purified by distillation is stored in a storage tank, and the purified product stored in the storage tank is passed through filters 1 to 5 shown in Table 1 in this order and filtered. Stored in tank.
- the object to be purified stored in the storage tank is filtered through the filters 6 to 7 shown in Table 1, and the object to be purified after being filtered through the filter 7 is circulated upstream of the filter 6, and then filtered again.
- a circulating filtration process of filtering at 6 to 7 was performed. After the circulation filtration treatment, the drug solution was stored in the container.
- water was added to the chemical so that the water content became a predetermined value.
- liquid contact parts of various devices for example, distillation towers, pipes, storage tanks, etc.
- various devices for example, distillation towers, pipes, storage tanks, etc.
- ⁇ Content of metal component The content of metal components (metal ions, metal-containing particles) in the chemical solution was measured by a method using ICP-MS and SP-ICP-MS. The following equipment was used. ⁇ Manufacturer: PerkinElmer ⁇ Model: NexION350S The following analysis software was used for the analysis. ⁇ Syngisix nano application module dedicated to “SP-ICP-MS” ⁇ Syngisix for ICP-MS software However, since the metal-containing particles of 10 nm or less cannot be measured by SP-ICP-MS, the above-mentioned specific method was used.
- GC / MS gas chromatography mass spectrometer
- ⁇ Test> (Pre-wet liquid or rinse liquid)
- a chemical solution is spin-discharged onto a silicon substrate having a diameter of 300 mm or a silicon substrate having a silicon oxide film having a diameter of 300 mm (a silicon substrate whose surface is covered with a silicon oxide film). Then, 0.5 cc of each chemical solution was discharged. Thereafter, the substrate was spin-dried. Next, using a wafer inspection apparatus “SP-5” manufactured by KLA-Tencor, the number of defects present on the substrate after the application of the chemical was measured (this is referred to as a measured value).
- the metal residue defect is a residue derived from a metal component
- the composite residue defect is a residue derived from a composite of an organic substance and a metal component
- the stain residue defect is a residue derived from an organic substance. If the “metal residue defect on Si” is “D” or more, it is suitably used as a pre-wet liquid or a rinsing liquid.
- a resist pattern was formed by the following operation.
- An actinic ray-sensitive or radiation-sensitive resin composition described below is applied to a silicon substrate having a diameter of 300 mm or a silicon substrate having a silicon oxide film having a diameter of 300 mm, and prebaked (PB) at 100 ° C. for 60 seconds.
- PB prebaked
- a resist film having a thickness of 150 nm was formed.
- Acid-decomposable resin represented by the following formula (weight average molecular weight (Mw): 7500): the numerical value described in each repeating unit means mol%): 100 parts by mass
- the polymer type quencher has a weight average molecular weight (Mw) of 5000.
- Mw weight average molecular weight
- Hydrophobic resin shown below 4 parts by mass (mass ratio was 0.5: 0.5 in order from the left)
- the hydrophobic resin on the left side has a weight average molecular weight. (Mw) is 7000, and the weight average molecular weight (Mw) of the right hydrophobic resin is 8000.
- the numerical value described in each repeating unit means a molar ratio.
- the wafer on which the resist film was formed was subjected to pattern exposure at 25 mJ / cm 2 using an ArF excimer laser scanner (Numerical Aperture: 0.75). Then, it heated at 120 degreeC for 60 second. Subsequently, each developing solution (chemical solution) was developed by paddle for 30 seconds. Next, the wafer was rotated at 4000 rpm for 30 seconds to form a negative resist pattern. Then, the obtained negative resist pattern was heated at 200 ° C. for 300 seconds. Through the above steps, an L / S pattern (average pattern width: 45 nm) having a line / space ratio of 1: 1 was obtained. In the space portion of the obtained sample, the presence or absence of the above-described metal residue defect, composite residue defect, and spot-like residue defect was evaluated according to the above method.
- the difference in pressure between the filters was 0.01 to 0.03 MPa.
- "Usage 1" in the “Usage” column means that the above test was carried out using the chemical solutions described in each of Examples and Comparative Examples as a pre-wet liquid and a rinsing liquid.
- “Use 2” in the “use” column means that the above test was performed using the chemicals described in each of the examples and comparative examples as a developer.
- “metal residue on Si” indicates the evaluation result of metal residue defect on the silicon substrate, and “composite residue on Si” indicates the result of composite residue defect on the silicon substrate.
- the “Ag ion amount (mass ppt)” column represents the silver ion content (mass ppt) with respect to the total mass of the chemical solution.
- the “metal component (mass ppt)” column indicates the content (mass ppt) of the metal component with respect to the total mass of the chemical solution.
- the column “Ag oxide particles / Ag ion” indicates a mass ratio of the content of silver oxide particles to the content of silver ions of 1.
- the “Pt ion amount (mass ppt)” column indicates the platinum ion content (mass ppt) with respect to the total mass of the chemical solution.
- the “Au ion amount (mass ppt)” column indicates the content (mass ppt) of gold ions with respect to the total mass of the chemical solution.
- the “number of Ti oxide particles” column indicates the number of titanium oxide particles in the chemical solution.
- the column “Ti oxide particles / Ag oxide particles” indicates the ratio of the content of titanium oxide particles to the content of silver oxide particles.
- the column “Ratio of Ag oxide particles (% by mass)” indicates the content (% by mass) of silver oxide particles with respect to the content of the silver component in the metal component.
- the column “Ratio of Ti oxide particles (% by mass)” indicates the content (% by mass) of the titanium oxide particles with respect to the content of the titanium component in the metal component.
- the column “Cu oxide particles / Cu ions” indicates the mass ratio of the content of Cu oxide particles to the content of Cu ions.
- the column “Fe oxide particles / Fe ions” indicates the mass ratio of the content of Fe oxide particles to the content of Fe ions.
- the column “Ratio of 0.5 to 17 nm Ti oxide particles (% by mass)” indicates the ratio (% by mass) of the titanium oxide particles having a particle size of 0.5 to 17 nm.
- the “moisture content” column indicates the water content (mass ppb) in the drug solution with respect to the total weight of the drug solution.
- E + number represents “10 numbers ”, for example, “3.5E + 04” represents “3.5 ⁇ 10 4 ”.
- “ ⁇ 1” represents less than 1.
- “ ⁇ 500 ppb” represents less than 500 mass ppb.
- Table 1 the data relating to each of the examples and the comparative examples are shown in Table 1 [Part 1] ⁇ 1> to ⁇ 6>, Table 1 [Part 2] ⁇ 1> to ⁇ 6>, Table 1 [Part 3] ⁇ 1> to ⁇ 6>, Table 1 [part 4] ⁇ 1> to ⁇ 6>, and Table 1 [part 5] ⁇ 1> to ⁇ 6>.
- Example 1 as shown in Table 1 [Part 1] ⁇ 1>, CyHe was used as the organic solvent, and as shown in Table 1 [Part 1] ⁇ 2>, the filter 2 was “IEX 15 nm”.
- the medicinal solution of the present invention could provide a predetermined effect.
- the content of silver ions is 0.0020 to 0.2% with respect to the total mass of the chemical solution.
- the content of the metal component was 10.0 to 500% by mass with respect to the total mass of the chemical solution. In the case of ppt, it was confirmed that the effect was more excellent.
- the effect is more excellent when the content of organic impurities is 1,000 to 100,000 mass ppt with respect to the total mass of the chemical solution. Was confirmed. Further, from Examples 1 and 2, it was confirmed that the effect was more excellent when the water content was 500 vol ppb or less.
- Example 29 After cleaning the container (EP-SUS) and various devices used in ⁇ Purification procedure> using the chemical solution (100 L) of Example 29, the separately prepared chemical solution of Example 29 was flowed into the above-described washed device, The solution was collected in a washed container, and a solution A was obtained in the container. After cleaning the container (EP-SUS) and various devices used in ⁇ Purification Procedure> using the chemical solution (100 L) of Example 40, the chemical solution of Example 29 prepared separately was poured into the washed device. Then, the solution was collected in a washed container, and a solution B was obtained in the container. When “metal residue defects on Si” was evaluated using solution A and solution B, better results were obtained with solution A.
- a resist composition 1 was obtained by mixing each component with the following composition.
- Photoacid generator (B-1) The following compounds were used as the photoacid generator (B-1).
- the resist composition 1 was applied on a silicon wafer having a diameter of 300 mm, and baked (PB: Prebake) at 100 ° C. for 60 seconds to form a resist film having a thickness of 30 nm.
- the resist film was exposed through a reflective mask using an EUV exposure machine (manufactured by ASML; NXE3350, NA 0.33, Dipole 90 °, outer sigma 0.87, inner sigma 0.35). Thereafter, heating (PEB: Post Exposure Bake) was performed at 85 ° C. for 60 seconds. Next, a developing solution (butyl acetate / manufactured by FETW) was sprayed for 30 seconds by a spray method for development, and a rinsing liquid was discharged onto a silicon wafer for 20 seconds by a spin coating method to be rinsed.
- EUV exposure machine manufactured by ASML; NXE3350, NA 0.33, Dipole 90 °, outer sigma 0.87, inner sigma 0.35.
- heating PEB: Post Exposure Bake
- a developing solution butyl acetate / manufactured by FETW
- a rinsing liquid was discharged onto a silicon wafer for 20 seconds by a spin coating method to be rinsed.
- the silicon wafer was rotated at a rotation speed of 2000 rpm for 40 seconds to form a line-and-space pattern having a space width of 20 nm and a pattern line width of 15 nm.
- the rinsing liquid the chemical used in Example 80 described above was used.
Abstract
Description
近年、フォトリソグラフィ技術の進歩によりパターンの微細化が進んでいる。パターンの微細化の手法としては、露光光源として、紫外線、KrFエキシマレーザー、ArFエキシマレーザー、及び、EUV(極紫外線)等を用いたパターン形成が試みられている。
形成されるパターンの微細化に伴い、このプロセスに用いる上記の薬液には更なる欠陥抑制性が求められている。 In the manufacture of a semiconductor device by a wiring forming process including photolithography, a pre-wet solution, a resist solution (composition for forming a resist film), a developing solution, a rinsing solution, a stripping solution, and chemical mechanical polishing (CMP). A chemical solution containing water and / or an organic solvent is used as a slurry, a cleaning solution after CMP, or a diluent thereof.
In recent years, miniaturization of patterns has been progressing due to the progress of photolithography technology. As a method of pattern miniaturization, pattern formation using an ultraviolet light, a KrF excimer laser, an ArF excimer laser, EUV (extreme ultraviolet light), or the like as an exposure light source has been attempted.
With the miniaturization of the pattern to be formed, the above-mentioned chemical solution used in this process is required to have further defect suppressing properties.
本発明は、シリコン基板と接触させた際に、金属残渣欠陥が生じにくい薬液を提供することを課題とする。
また、本発明は、薬液収容体を提供することも課題とする。 On the other hand, in recent years, there has been a demand for a chemical solution that is less likely to cause metal residue defects on the silicon substrate when the silicon substrate is brought into contact with the chemical solution.
An object of the present invention is to provide a chemical solution that is less likely to cause metal residue defects when brought into contact with a silicon substrate.
Another object of the present invention is to provide a drug solution container.
金属成分が、銀イオンを含有し、
銀イオンの含有量が、薬液全質量に対して、0.0010~1.0質量pptである、薬液。
(2) 金属成分の含有量が、薬液全質量に対して、10.0~500質量pptである、(1)に記載の薬液。
(3) 金属成分が酸化銀粒子を含有し、
銀イオンの含有量に対する、酸化銀粒子の含有量の質量比1が、0.00000010~0.1である、(2)に記載の薬液。
(4) 酸化銀粒子の含有量が、金属成分中の銀成分の含有量に対して、0.00010~5.0質量%である、(3)に記載の薬液。
(5) 金属成分が、酸化チタン粒子、及び、チタンイオンを含有し、
チタンイオンの含有量に対する、酸化チタン粒子の含有量の質量比2と、質量比1とが以下の式(A)の関係を満たす、(3)又は(4)に記載の薬液。
式(A) 質量比2>質量比1
(6) 酸化銀粒子の含有量に対する、酸化チタン粒子の含有量の比が102~1010である、(5)に記載の薬液。
(7) 酸化チタン粒子の数が、102~1010個である、(5)又は(6)に記載の薬液。
(8) 酸化チタン粒子の含有量が、金属成分中のチタン成分の含有量に対して、5質量%以上98質量%未満である、(5)~(7)のいずれかに記載の薬液。
(9) 酸化チタン粒子のうち、粒径0.5~17nmである粒子の割合が、40質量%以上99質量%未満である、(5)~(8)のいずれかに記載の薬液。
(10) 金属成分が、酸化銅粒子、及び、銅イオンを含有し、
銅イオンの含有量に対する、酸化銅粒子の含有量の質量比3と、質量比1とが以下の式(B)の関係を満たす、(3)~(9)のいずれかに記載の薬液。
式(B) 質量比3>質量比1
(11) 金属成分が、酸化鉄粒子、及び、鉄イオンを含有し、
鉄イオンの含有量に対する、酸化鉄粒子の含有量の質量比4と、質量比1とが以下の式(C)の関係を満たす、(3)~(9)のいずれかに記載の薬液。
式(C) 質量比4>質量比1
(12) 金属成分が、白金イオンを含有し、
白金イオンの含有量が、薬液全質量に対して、0.000010~1.0質量pptである、(1)~(11)のいずれかに記載の薬液。
(13) 金属成分が、金イオンを含有し、
金イオンの含有量が、薬液全質量に対して、0.00010~1.0質量pptである、(1)~(12)のいずれかに記載の薬液。
(14) 更に、有機不純物を含有し、
有機不純物の含有量が、薬液全質量に対して、1000~100000質量pptである、(1)~(13)のいずれかに記載の薬液。
(15) 薬液全質量に対する水の含有量が500質量ppb以下である、(1)~(14)のいずれかに記載の薬液。
(16) 有機溶剤が、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、シクロヘキサノン、乳酸エチル、炭酸プロピレン、イソプロパノール、4-メチル-2-ペンタノール、酢酸ブチル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、メトキシプロピオン酸メチル、シクロペンタノン、γ-ブチロラクトン、ジイソアミルエーテル、酢酸イソアミル、ジメチルスルホキシド、N-メチルピロリドン、ジエチレングリコール、エチレングリコール、ジプロピレングリコール、プロピレングリコール、炭酸エチレン、スルフォラン、シクロヘプタノン、2-ヘプタノン、酪酸ブチル、イソ酪酸イソブチル、イソアミルエーテル、及び、ウンデカンからなる群から選ばれる1種以上を含む、(1)~(15)のいずれかに記載の薬液。
(17) 容器と、容器に収容された(1)~(16)のいずれかに記載の薬液と、を含有する、薬液収容体。 (1) A chemical solution containing an organic solvent and a metal component,
The metal component contains silver ions,
A chemical solution having a silver ion content of 0.0010 to 1.0 mass ppt, based on the total mass of the chemical solution.
(2) The chemical according to (1), wherein the content of the metal component is 10.0 to 500 mass ppt based on the total mass of the chemical.
(3) the metal component contains silver oxide particles,
The chemical solution according to (2), wherein the mass ratio 1 of the content of silver oxide particles to the content of silver ions is from 0.000000010 to 0.1.
(4) The chemical solution according to (3), wherein the content of the silver oxide particles is 0.00010 to 5.0% by mass based on the content of the silver component in the metal component.
(5) The metal component contains titanium oxide particles and titanium ions,
The chemical solution according to (3) or (4), wherein the mass ratio 2 of the content of the titanium oxide particles to the content of titanium ions and the mass ratio 1 satisfy the relationship of the following formula (A).
Formula (A) Mass ratio 2> Mass ratio 1
(6) The chemical solution according to (5), wherein the ratio of the content of the titanium oxide particles to the content of the silver oxide particles is 10 2 to 10 10 .
(7) The chemical solution according to (5) or (6), wherein the number of titanium oxide particles is 10 2 to 10 10 .
(8) The chemical solution according to any of (5) to (7), wherein the content of the titanium oxide particles is 5% by mass or more and less than 98% by mass with respect to the content of the titanium component in the metal component.
(9) The drug solution according to any of (5) to (8), wherein the proportion of the titanium oxide particles having a particle size of 0.5 to 17 nm is from 40% by mass to less than 99% by mass.
(10) The metal component contains copper oxide particles and copper ions,
The chemical solution according to any one of (3) to (9), wherein the mass ratio of the content of copper oxide particles to the content of copper ions and the mass ratio satisfy the relationship of the following formula (B).
Formula (B) Mass ratio 3> Mass ratio 1
(11) The metal component contains iron oxide particles and iron ions,
The chemical solution according to any one of (3) to (9), wherein the mass ratio of the content of the iron oxide particles to the content of iron ions and the mass ratio satisfy the relationship of the following formula (C).
Formula (C) Mass ratio 4> Mass ratio 1
(12) The metal component contains a platinum ion,
The chemical solution according to any one of (1) to (11), wherein the content of platinum ions is 0.000010 to 1.0 mass ppt based on the total mass of the chemical solution.
(13) The metal component contains gold ions,
The chemical solution according to any one of (1) to (12), wherein the content of the gold ion is 0.00010 to 1.0 mass ppt based on the total mass of the chemical solution.
(14) It further contains organic impurities,
The chemical solution according to any one of (1) to (13), wherein the content of the organic impurities is 1,000 to 100,000 mass ppt based on the total mass of the chemical solution.
(15) The drug solution according to any one of (1) to (14), wherein the content of water with respect to the total weight of the drug solution is 500 mass ppb or less.
(16) The organic solvent is propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, propylene carbonate, isopropanol, 4-methyl-2-pentanol, butyl acetate, propylene glycol monoethyl ether, propylene glycol monopropyl Ether, methyl methoxypropionate, cyclopentanone, γ-butyrolactone, diisoamyl ether, isoamyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cycloheptanone , 2-heptanone, butyl butyrate, isobutyl isobutyrate, isoamyl ether and undecane It made containing one or more selected from the group drug solution according to any one of (1) to (15).
(17) A drug solution container, comprising a container and the drug solution according to any one of (1) to (16) stored in the container.
また、本発明によれば、薬液収容体を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, when it is made to contact with a silicon substrate, the chemical liquid which a metal residue defect does not generate easily can be provided.
Further, according to the present invention, a drug solution container can be provided.
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形態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形態に限定されない。
なお、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及び上限値として含む範囲を意味する。
また、本発明において、「ppm」は「parts-per-million(10-6)」を意味し、「ppb」は「parts-per-billion(10-9)」を意味し、「ppt」は「parts-per-trillion(10-12)」を意味し、「ppq」は「parts-per-quadrillion(10-15)」を意味する。
また、本発明における基(原子群)の表記において、置換及び無置換を記していない表記は、本発明の効果を損ねない範囲で、置換基を有さない基と共に置換基を含有する基をも包含する。例えば、「炭化水素基」とは、置換基を有さない炭化水素基(無置換炭化水素基)のみならず、置換基を含有する炭化水素基(置換炭化水素基)をも包含する。この点は、各化合物についても同義である。
また、本発明における「放射線」とは、例えば、遠紫外線、極紫外線(EUV;Extreme ultraviolet)、X線、又は、電子線等を意味する。また、本発明において光とは、活性光線又は放射線を意味する。本発明中における「露光」とは、特に断らない限り、遠紫外線、X線又はEUV等による露光のみならず、電子線又はイオンビーム等の粒子線による描画も露光に含める。 Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In addition, in this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
In the present invention, “ppm” means “parts-per-million (10 −6 )”, “ppb” means “parts-per-billion (10 −9 )”, and “ppt” means “Parts-per-trillion (10 −12 )” means “parts-per-quadrillion (10 −15 )”.
Further, in the notation of the group (atom group) in the present invention, the notation that does not indicate substitution or unsubstitution means a group containing a substituent together with a group having no substituent within a range not impairing the effect of the present invention. Is also included. For example, the “hydrocarbon group” includes not only a hydrocarbon group having no substituent (unsubstituted hydrocarbon group) but also a hydrocarbon group having a substituent (substituted hydrocarbon group). This is the same for each compound.
Further, “radiation” in the present invention means, for example, far ultraviolet rays, extreme ultraviolet (EUV), X-rays, or electron beams. In the present invention, light means actinic rays or radiation. Unless otherwise specified, the term “exposure” in the present invention includes not only exposure with far ultraviolet rays, X-rays or EUV, but also drawing with particle beams such as electron beams or ion beams.
本発明者らは、薬液が銀イオンを含有する際に、その含有量によってシリコン基板上での金属残渣欠陥(金属成分由来の残渣)の生じやすさが異なることを知見している。より具体的には、銀イオンの量が所定値超の場合、多くの銀イオンが存在するため、銀イオンがシリコン基板上で還元されて、多量の銀粒子がシリコン基板上に付着し、金属残渣欠陥が生じていると考えられる。一方で、銀イオンの量が所定値未満の場合、有機物又は他のイオンとの衝突頻度が下がり、結果としてシリコン基板との反応の可能性が高まり、結果として金属残渣欠陥が生じていると考えられる。それに対して、銀イオンの量が所定範囲である場合、有機物又は他のイオンとの衝突頻度が増えて、結果として各種複合体となって、シリコン基板上での還元反応に使用される銀イオンの量が低下し、金属残渣欠陥ができにくくなっていると考えられる。 Although the mechanism by which the above-mentioned problem is solved by the chemical solution of the present invention is not always clear, the present inventors presume the mechanism as follows. In addition, the following mechanism is speculation, and even when the effect of the present invention is obtained by a different mechanism, it is included in the scope of the present invention.
The present inventors have found that when a chemical solution contains silver ions, the likelihood of metal residue defects (residues derived from metal components) on a silicon substrate varies depending on the content of silver ions. More specifically, when the amount of silver ions exceeds a predetermined value, many silver ions are present, so that the silver ions are reduced on the silicon substrate, and a large amount of silver particles adhere to the silicon substrate, and It is considered that residue defects have occurred. On the other hand, when the amount of silver ions is less than the predetermined value, it is considered that the frequency of collision with organic substances or other ions decreases, and as a result, the possibility of reaction with the silicon substrate increases, and as a result, metal residue defects are generated. Can be On the other hand, when the amount of silver ions is within a predetermined range, the frequency of collision with organic substances or other ions increases, resulting in various complexes, and silver ions used for the reduction reaction on the silicon substrate. It is considered that the amount of the metal residue is reduced, and it is difficult to generate metal residue defects.
以下、本発明の薬液に含まれる成分について詳述する。 The chemical solution of the present invention is a chemical solution containing an organic solvent and a metal component, wherein the metal component contains silver ions, and the content of silver ions is 0.0010 to 1.0. 0 mass ppt.
Hereinafter, the components contained in the chemical solution of the present invention will be described in detail.
本発明の薬液(以下、単に「薬液」ともいう)は、有機溶剤を含有する。
本明細書において、有機溶剤とは、上記薬液の全質量に対して、1成分あたり10000質量ppmを超えた含有量で含有される液状の有機化合物を意図する。つまり、本明細書においては、上記薬液の全質量に対して10000質量ppmを超えて含有される液状の有機化合物は、有機溶剤に該当する。
また、本明細書において液状とは、25℃、大気圧下において、液体であることを意味する。 <Organic solvent>
The chemical solution of the present invention (hereinafter, also simply referred to as “chemical solution”) contains an organic solvent.
In the present specification, an organic solvent is intended to mean a liquid organic compound contained at a content exceeding 10,000 mass ppm per component with respect to the total mass of the chemical solution. That is, in this specification, a liquid organic compound contained in an amount exceeding 10,000 ppm by mass with respect to the total mass of the chemical solution corresponds to an organic solvent.
In addition, in the present specification, the term “liquid” means a liquid at 25 ° C. and atmospheric pressure.
有機溶剤は1種を単独で用いても、2種以上を使用してもよい。2種以上の有機溶剤を使用する場合には、合計含有量が上記範囲内であるのが好ましい。 The content of the organic solvent in the chemical solution is not particularly limited, but is preferably 98.0% by mass or more, more preferably more than 99.0% by mass, and more preferably 99.90% by mass or more based on the total mass of the chemical solution. Preferably, it is more than 99.95% by mass. The upper limit is less than 100% by mass.
One type of organic solvent may be used alone, or two or more types may be used. When two or more organic solvents are used, the total content is preferably within the above range.
有機溶剤を2種以上使用する例としては、PGMEAとPGMEの併用、及び、PGMEAとPCの併用が挙げられる。
なお、薬液中における有機溶剤の種類及び含有量は、ガスクロマトグラフ質量分析計を用いて測定できる。 Examples of the organic solvent include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), propylene carbonate (PC), isopropanol (IPA), and 4-methyl-2. -Pentanol (MIBC), butyl acetate (nBA), propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl methoxypropionate, cyclopentanone, γ-butyrolactone, diisoamyl ether, isoamyl acetate, dimethyl sulfoxide, N- Methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cycloheptanone, Heptanone, butyl butyrate, isobutyl isobutyrate, isoamyl ether, and one or more selected from the group consisting of undecane is preferred.
Examples of using two or more organic solvents include a combination of PGMEA and PGME, and a combination of PGMEA and PC.
In addition, the kind and content of the organic solvent in the chemical solution can be measured using a gas chromatograph mass spectrometer.
薬液は金属成分を含有する。
金属成分は、金属含有粒子及び金属イオンから構成され、例えば、金属成分の含有量という場合、金属含有粒子及び金属イオンの合計含有量を示す。
金属含有粒子は、金属原子が含まれていればよく、例えば、金属酸化物粒子、金属窒化物粒子、及び、金属粒子が挙げられる。なお、金属粒子とは、金属のみからなる粒子を意味する。 <Metal components>
The chemical solution contains a metal component.
The metal component is composed of metal-containing particles and metal ions. For example, the content of the metal component indicates the total content of the metal-containing particles and metal ions.
The metal-containing particles only need to include metal atoms, and examples thereof include metal oxide particles, metal nitride particles, and metal particles. The metal particles mean particles composed of only metal.
銀イオンの含有量は、薬液全質量に対して、0.0010~1.0質量pptであり、シリコン基板上に金属残渣欠陥がより生じにくい点で、0.0020~0.90質量pptが好ましく、0.05~0.90質量pptがより好ましく、0.10~0.90質量pptが更に好ましい。 The metal component contained in the chemical solution contains silver ions.
The content of silver ions is 0.0010 to 1.0 mass ppt with respect to the total mass of the chemical solution, and 0.0020 to 0.90 mass ppt is low in that metal residue defects are less likely to occur on the silicon substrate. Preferably, 0.05 to 0.90 mass ppt is more preferable, and 0.10 to 0.90 mass ppt is more preferable.
薬液に酸化銀粒子が含有される場合、銀イオンの含有量に対する、酸化銀粒子の含有量の質量比1(酸化銀粒子の含有量/銀イオンの含有量)は特に制限されず、0.000000010~1.5の場合が多い。中でも、シリコン基板上又は酸化ケイ素膜上に、金属残渣欠陥又は後述する複合物残渣欠陥がより生じにくい点で、上記質量比1は、0.00000010~0.1が好ましく、0.000001~0.01がより好ましく、0.00001~0.005が更に好ましい。 The metal component contained in the chemical solution may contain silver oxide particles.
When the chemical solution contains silver oxide particles, the mass ratio of the content of silver oxide particles to the content of silver ions (1) (content of silver oxide particles / content of silver ions) is not particularly limited. 000000010 to 1.5 in many cases. Above all, the mass ratio 1 is preferably from 0.000000010 to 0.1, and more preferably from 0.000001 to 0, in that metal residue defects or composite residue defects described later are less likely to occur on a silicon substrate or a silicon oxide film. 0.01 and more preferably 0.00001 to 0.005.
なお、銀成分とは、銀原子を含有する成分であり、銀含有粒子及び銀イオンから構成され、例えば、銀成分の含有量という場合、銀含有粒子及び銀イオンの合計含有量を示す。
銀含有粒子は、銀原子が含まれていればよく、例えば、酸化銀粒子、窒化銀粒子、及び、銀粒子が挙げられる。なお、銀粒子とは、金属銀からなる粒子を意味する。 The content of the silver oxide particles is not particularly limited, and is often 0.00001 to 10% by mass based on the content of the silver component in the metal component. Among them, the content of silver oxide particles is preferably from 0.00010 to 5.0% by mass, more preferably from 0.010 to 1% by mass, based on the content of the silver component in the metal component, in that the effect of the present invention is more excellent. 0.0% by mass is more preferred.
The silver component is a component containing a silver atom and is composed of silver-containing particles and silver ions. For example, when the content of the silver component is referred to, it indicates the total content of the silver-containing particles and silver ions.
The silver-containing particles only need to contain silver atoms, and examples thereof include silver oxide particles, silver nitride particles, and silver particles. The silver particles mean particles made of metallic silver.
薬液に含有される金属成分は、チタン成分を含有していてもよい。チタン成分とは、チタン原子を含有する成分であり、チタン含有粒子及びチタンイオンから構成され、例えば、チタン成分の含有量という場合、チタン含有粒子及びチタンイオンの合計含有量を示す。
チタン含有粒子は、チタン原子が含まれていればよく、例えば、酸化チタン粒子、窒化チタン粒子、及び、チタン粒子が挙げられる。なお、チタン粒子とは、金属チタンからなる粒子を意味する。 The metal component contained in the chemical solution may contain components other than the silver component.
The metal component contained in the chemical solution may contain a titanium component. The titanium component is a component containing a titanium atom, and is composed of titanium-containing particles and titanium ions. For example, when referring to the content of the titanium component, it indicates the total content of the titanium-containing particles and titanium ions.
The titanium-containing particles only need to contain titanium atoms, and examples thereof include titanium oxide particles, titanium nitride particles, and titanium particles. The titanium particles mean particles made of titanium metal.
チタンイオンの含有量に対する、酸化チタン粒子の含有量の質量比2(酸化チタン粒子の含有量/チタンイオンの含有量)は特に制限されないが、上述した質量比1と以下の式(A)の関係を満たすことが好ましい。
式(A) 質量比2>質量比1 The metal component contained in the chemical solution may contain titanium oxide particles and titanium ions.
The mass ratio 2 of the content of the titanium oxide particles to the content of the titanium ions (content of the titanium oxide particles / content of the titanium ions) is not particularly limited, but the mass ratio 1 described above and the following formula (A) It is preferable to satisfy the relationship.
Formula (A) Mass ratio 2> Mass ratio 1
酸化チタン粒子のうち、粒径0.5~17nmである粒子の割合は特に制限されず、30~99質量%の場合が多い。中でも、シリコン基板上又は酸化ケイ素膜上に、金属残渣欠陥又は後述する複合物残渣欠陥がより生じにくい点で、酸化チタン粒子のうち、粒径0.5~17nmである粒子の割合は、40質量%以上99質量%未満が好ましく、70~98質量%がより好ましい。 The content of the titanium oxide particles is not particularly limited, and is often 1 to 99% by mass based on the content of the titanium component in the metal component. Among them, on the silicon substrate or on the silicon oxide film, metal residue defects or composite residue defects described below are less likely to occur, the content of the titanium oxide particles is relative to the content of the titanium component in the metal component. It is preferably from 5% by mass to less than 98% by mass, more preferably from 10 to 90% by mass.
The proportion of the titanium oxide particles having a particle size of 0.5 to 17 nm is not particularly limited, and is often 30 to 99% by mass. Above all, the ratio of particles having a particle size of 0.5 to 17 nm among titanium oxide particles is 40% because metal residue defects or composite residue defects described later are less likely to be formed on a silicon substrate or a silicon oxide film. It is preferably at least 70% by mass and less than 99% by mass, more preferably 70 to 98% by mass.
白金イオンの含有量は特に制限されず、薬液全質量に対して、0.000001~1.5質量pptの場合が多い。中でも、シリコン基板上に、金属残渣欠陥又は後述する複合物残渣欠陥がより生じにくい点で、白金イオンの含有量は、薬液全質量に対して、0.000010~1.0質量pptが好ましく、0.00010~0.50質量pptがより好ましく、0.001質量%以上0.20質量ppt未満が更に好ましい。
薬液に含有される金属成分は、金イオンを含有していてもよい。
金イオンの含有量は特に制限されず、薬液全質量に対して、0.000001~1.5質量pptの場合が多い。中でも、シリコン基板上に、金属残渣欠陥又は後述する複合物残渣欠陥がより生じにくい点で、金イオンの含有量は、薬液全質量に対して、0.000010~1.0質量pptが好ましく、0.00010~1.0質量pptがより好ましく、0.001質量%以上0.10質量ppt未満が更に好ましい。 The metal component contained in the chemical solution may contain platinum ions.
The content of platinum ions is not particularly limited, and is often 0.000001 to 1.5 mass ppt based on the total mass of the chemical solution. Above all, the content of platinum ions is preferably 0.000010 to 1.0 mass ppt, based on the total mass of the chemical solution, in that metal residue defects or composite residue defects described below are less likely to occur on the silicon substrate. 0.00010 to 0.50 mass ppt is more preferable, and more preferably 0.001% by mass or more and less than 0.20 mass ppt.
The metal component contained in the chemical solution may contain gold ions.
The content of the gold ion is not particularly limited, and is often 0.000001 to 1.5 mass ppt based on the total mass of the chemical solution. Among them, the content of gold ions is preferably 0.000010 to 1.0 mass ppt, based on the total mass of the chemical solution, in that metal residue defects or composite residue defects described below are less likely to occur on the silicon substrate. 0.00010 to 1.0 mass ppt is more preferable, and 0.001 mass% or more and less than 0.10 mass ppt is more preferable.
他の金属原子としては、例えば、Na(ナトリウム)、K(カリウム)、Ca(カルシウム)、Fe(鉄)、Cu(銅)、Mg(マグネシウム)、Mn(マンガン)、Li(リチウム)、Al(アルミニウム)、Cr(クロム)、Ni(ニッケル)、及び、Zn(ジルコニウム)が挙げられる。 The metal component contained in the chemical solution may contain components of other metal atoms than those described above.
Other metal atoms include, for example, Na (sodium), K (potassium), Ca (calcium), Fe (iron), Cu (copper), Mg (magnesium), Mn (manganese), Li (lithium), Al (Aluminum), Cr (chromium), Ni (nickel), and Zn (zirconium).
銅イオンの含有量に対する、酸化銅粒子の含有量の質量比3(酸化銅粒子の含有量/銅イオンの含有量)は特に制限されないが、上述した質量比1と以下の式(B)の関係を満たすことが好ましい。
式(B) 質量比3>質量比1
薬液に含有される金属成分は、酸化鉄粒子、及び、鉄イオンを含有していてもよい。
鉄イオンの含有量に対する、酸化鉄粒子の含有量の質量比4(酸化鉄粒子の含有量/鉄イオンの含有量)は特に制限されないが、上述した質量比1と以下の式(C)の関係を満たすことが好ましい。
式(C) 質量比4>質量比1 The metal component contained in the chemical solution may contain copper oxide particles and copper ions.
The mass ratio 3 of the content of the copper oxide particles to the content of the copper ions (the content of the copper oxide particles / the content of the copper ions) is not particularly limited, but the mass ratio 1 described above and the following formula (B) It is preferable to satisfy the relationship.
Formula (B) Mass ratio 3> Mass ratio 1
The metal component contained in the chemical solution may contain iron oxide particles and iron ions.
The mass ratio 4 of the content of iron oxide particles to the content of iron ions (content of iron oxide particles / content of iron ions) is not particularly limited, but the mass ratio 1 described above and the following formula (C) are used. It is preferable to satisfy the relationship.
Formula (C) Mass ratio 4> Mass ratio 1
ここで、SP-ICP-MS法とは、通常のICP-MS法(誘導結合プラズマ質量分析法)と同様の装置を使用し、データ分析のみが異なる。SP-ICP-MS法のデータ分析は、市販のソフトウェアにより実施できる。
ICP-MS法では、測定対象とされた金属成分の含有量が、その存在形態に関わらず、測定される。従って、測定対象とされた金属含有粒子と、金属イオンとの合計質量が、金属成分の含有量として定量される。 Note that the types and contents of metal ions and metal-containing particles in a chemical solution can be measured by an SP-ICP-MS method (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry).
Here, the SP-ICP-MS method uses an apparatus similar to a normal ICP-MS method (inductively coupled plasma mass spectrometry), and differs only in data analysis. Data analysis of the SP-ICP-MS method can be performed by commercially available software.
In the ICP-MS method, the content of a metal component to be measured is measured regardless of its existing form. Therefore, the total mass of the metal-containing particles to be measured and the metal ions is determined as the content of the metal component.
SP-ICP-MS法の装置としては、例えば、アジレントテクノロジー社製、Agilent 8800 トリプル四重極ICP-MS(inductively coupled plasma mass spectrometry、半導体分析用、オプション#200)が挙げられ、実施例に記載した方法により測定できる。上記以外の他の装置としては、PerkinElmer社製 NexION350Sのほか、アジレントテクノロジー社製、Agilent 8900も使用できる。 On the other hand, in the SP-ICP-MS method, the content of metal-containing particles can be measured. Therefore, by subtracting the content of the metal-containing particles from the content of the metal component in the sample, the content of the metal ion in the sample can be calculated.
As an apparatus of the SP-ICP-MS method, for example, Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, option # 200 for semiconductor analysis, option # 200) manufactured by Agilent Technologies, Inc. is described in Examples. Can be measured by the following method. As an apparatus other than the above, in addition to NexION350S manufactured by PerkinElmer, Agilent 8900 manufactured by Agilent Technologies can be used.
ここで特定方法により、基板上に残った0.5~10nmの粒子数をカウントし、そのカウントに対し、20nmの粒子のSNP-ICP-MSからの換算値を用いる。ここで金属毎に換算値が異なる為に金属毎にこの換算を行う。
換算の具体的方法は以下のとおりである。
例えば、薬液中の20nmの酸化チタン粒子の数がSNP-ICP-MSで10個であり、特定方法で算出される基板上に残った20nmの酸化チタン粒子の数が1個の場合、換算値は10になる。つまり、特定方法で確認できた1nmの酸化チタン粒子の数が100個の場合には、換算値の10倍を元にして、薬液中では1000個(100個×10)と計算する。本発明における10nm以下の粒子数はいずれの金属であれ、この換算方法によって推定する。 In addition, since the metal-containing particles of 10 nm or less cannot be measured by SP-ICP-MS, the method described in paragraphs 0015 to 0067 of JP-A-2009-188333 (hereinafter, also referred to as “specific method”) is used.
Here, the number of particles of 0.5 to 10 nm remaining on the substrate is counted by a specific method, and the converted value of the 20 nm particles from SNP-ICP-MS is used for the count. Here, since the conversion value differs for each metal, this conversion is performed for each metal.
The specific method of conversion is as follows.
For example, if the number of 20 nm titanium oxide particles in the chemical solution is 10 by SNP-ICP-MS and the number of 20 nm titanium oxide particles remaining on the substrate calculated by the specific method is 1, the converted value Becomes 10. That is, when the number of 1 nm titanium oxide particles confirmed by the specific method is 100, the number is calculated as 1000 (100 × 10) in the chemical based on 10 times the converted value. The number of particles having a size of 10 nm or less in the present invention is estimated by this conversion method regardless of the type of metal.
薬液は有機不純物を含有してもよい。
薬液中における有機不純物の含有量は特に制限されないが、シリコン基板上に、後述するシミ状残渣欠陥がより生じにくい点で、薬液全質量に対して、1000~100000質量pptが好ましい。
なお、有機不純物とは、有機溶剤とは異なる有機化合物であって、有機溶剤の全質量に対して、10000質量ppm以下の含有量で含有される有機化合物を意味する。つまり、本明細書においては、上記有機溶剤の全質量に対して10000質量ppm以下の含有量で含有される有機化合物は、有機不純物に該当し、有機溶剤には該当しないものとする。
有機不純物は、被精製物を精製して薬液を得る過程で、薬液に混入する、又は、添加されることが多い。そのような有機不純物としては、例えば、可塑剤、酸化防止剤、及び、これらに由来する化合物(典型的には分解生成物)等が挙げられる。 <Organic impurities>
The chemical may contain organic impurities.
The content of the organic impurities in the chemical solution is not particularly limited, but is preferably from 1,000 to 100,000 mass ppt based on the total mass of the chemical solution from the viewpoint that stain-like residue defects described later are less likely to be formed on the silicon substrate.
Note that the organic impurity is an organic compound different from the organic solvent, and means an organic compound contained at a content of 10000 ppm by mass or less based on the total mass of the organic solvent. That is, in the present specification, an organic compound contained at a content of 10,000 mass ppm or less based on the total mass of the organic solvent corresponds to an organic impurity and does not correspond to an organic solvent.
Organic impurities are often mixed with or added to a chemical solution during the process of refining a substance to be purified to obtain a chemical solution. Examples of such organic impurities include a plasticizer, an antioxidant, and a compound derived from these (typically, a decomposition product).
薬液は、水を含有してもよい。水は、上記有機不純物には含まれない。
水としては特に制限されず、例えば、蒸留水、イオン交換水、及び、純水等を使用できる。
水は、薬液中に添加されてもよいし、薬液の製造工程において意図せずに薬液中に混合されてもよい。薬液の製造工程において意図せずに混合される場合としては、例えば、水が、薬液の製造に用いる原料(例えば、有機溶剤)に含有されている場合、及び、薬液の製造工程で混合する(例えば、コンタミネーション)等が挙げられるが、上記に制限されない。 <Water>
The drug solution may contain water. Water is not included in the organic impurities.
The water is not particularly limited, and for example, distilled water, ion-exchanged water, pure water, and the like can be used.
Water may be added to the chemical solution, or may be unintentionally mixed into the chemical solution in the process of manufacturing the chemical solution. Examples of the case of being unintentionally mixed in the manufacturing process of the chemical solution include, for example, the case where water is contained in a raw material (for example, an organic solvent) used for manufacturing the chemical solution, and the mixing in the manufacturing process of the chemical solution ( For example, contamination) is not limited to the above.
本発明の薬液は、半導体デバイスの製造に用いられるのが好ましい。中でも、本発明の薬液を用いて半導体チップを製造することが好ましい。
具体的には、リソグラフィー工程、エッチング工程、イオン注入工程、及び、剥離工程等を含有する半導体デバイスの製造工程において、各工程の終了後、又は、次の工程に移る前に、有機物を処理するために使用され、具体的にはプリウェット液、現像液、リンス液、及び、研磨液等として好適に用いられる。
他にも、薬液は、レジスト膜形成用組成物が含有する樹脂の希釈液等(言い換えれば、溶剤)としても用いてもよい。 <Use of chemicals>
The chemical solution of the present invention is preferably used for manufacturing a semiconductor device. Especially, it is preferable to manufacture a semiconductor chip using the chemical solution of the present invention.
Specifically, in a semiconductor device manufacturing process including a lithography process, an etching process, an ion implantation process, and a peeling process, an organic material is processed after each process or before moving to the next process. Specifically, it is suitably used as a pre-wet liquid, a developing liquid, a rinsing liquid, a polishing liquid or the like.
In addition, the chemical solution may be used as a diluting solution of the resin contained in the resist film forming composition (in other words, a solvent).
また、上記薬液は、医療用途又は洗浄用途の溶剤としても使用できる。例えば、配管、容器、及び、基板(例えば、ウェハ、及び、ガラス等)等の洗浄に好適に使用できる。
上記洗浄用途としては、上述のプリウェット液等の液が接する配管及び容器等を洗浄する、洗浄液(配管洗浄液及び容器洗浄液等)として使用するのも好ましい。 In addition, the above-mentioned chemical solution can be used for other uses other than the production of semiconductor devices, and can also be used as a developer and a rinse for polyimide, a resist for sensors, a resist for lenses, and the like.
Further, the above chemical solution can be used as a solvent for medical use or cleaning use. For example, it can be suitably used for cleaning pipes, containers, and substrates (for example, wafers and glass).
As the above-mentioned cleaning use, it is also preferable to use as a cleaning liquid (a pipe cleaning liquid and a container cleaning liquid, etc.) for cleaning pipes, containers, and the like that come into contact with a liquid such as the above-mentioned pre-wet liquid.
上記薬液の製造方法としては特に制限されず、公知の製造方法が使用できる。中でも、より優れた本発明の効果を示す薬液が得られる点で、薬液の製造方法は、フィルターを用いて、有機溶剤を含有する被精製物をろ過して薬液を得る、ろ過工程を有するのが好ましい。 <Chemical liquid manufacturing method>
The method for producing the chemical solution is not particularly limited, and a known production method can be used. Above all, in that a drug solution exhibiting a better effect of the present invention can be obtained, the method for producing a drug solution has a filtration step of filtering a substance to be purified containing an organic solvent using a filter to obtain a drug solution. Is preferred.
より具体的には、例えば、酢酸とn-ブタノールとを硫酸の存在下で反応させ、酢酸ブチルを得る方法;エチレン、酸素、及び、水をAl(C2H5)3の存在下で反応させ、1-ヘキサノールを得る方法;シス-4-メチル-2-ペンテンをIpc2BH(Diisopinocampheylborane)の存在下で反応させ、4-メチル-2-ペンタノールを得る方法;プロピレンオキシド、メタノール、及び、酢酸を硫酸の存在下で反応させ、PGMEA(プロピレングリコール1-モノメチルエーテル2-アセタート)を得る方法;アセトン、及び、水素を酸化銅-酸化亜鉛-酸化アルミニウムの存在下で反応させて、IPA(isopropyl alcohol)を得る方法;乳酸、及び、エタノールを反応させて、乳酸エチルを得る方法;等が挙げられる。 There is no particular limitation on the method of obtaining the object to be purified (typically, the object to be purified containing an organic solvent) by reacting the raw materials, and a known method can be used. For example, there is a method in which one or more raw materials are reacted in the presence of a catalyst to obtain an organic solvent.
More specifically, for example, a method of reacting acetic acid and n-butanol in the presence of sulfuric acid to obtain butyl acetate; reacting ethylene, oxygen, and water in the presence of Al (C 2 H 5 ) 3 Reacting cis-4-methyl-2-pentene in the presence of Ipc2BH (Diisopinocampheylborane) to obtain 4-methyl-2-pentanol; propylene oxide, methanol and acetic acid Is reacted in the presence of sulfuric acid to obtain PGMEA (propylene glycol 1-monomethyl ether 2-acetate); acetone and hydrogen are reacted in the presence of copper oxide-zinc oxide-aluminum oxide to give IPA (isopropyl). alcohol) by reacting lactic acid and ethanol to obtain lactic acid. And the like; a method of obtaining a chill.
本発明の薬液の製造方法は、フィルターを用いて上記被精製物をろ過して薬液を得るろ過工程を有することが好ましい。フィルターを用いて被精製物をろ過する方法としては特に制限されないが、ハウジングと、ハウジングに収納されたフィルターカートリッジと、を有するフィルターユニットに、被精製物を加圧又は無加圧で通過させる(通液する)のが好ましい。 (Filtration process)
The method for producing a drug solution of the present invention preferably includes a filtration step of filtering the above-mentioned substance to be purified using a filter to obtain a drug solution. The method of filtering the object to be purified using a filter is not particularly limited, and the object to be purified is passed through a filter unit having a housing and a filter cartridge housed in the housing with or without pressurization ( Is preferable.
フィルターの細孔径としては特に制限されず、被精製物のろ過用として通常使用される細孔径のフィルターが使用できる。中でも、フィルターの細孔径は、薬液が含有する粒子(金属粒子等)の数を所望の範囲により制御しやすい点で、200nm以下が好ましく、20nm以下がより好ましく、10nm以下が更に好ましく、5nm以下が特に好ましい。下限値としては特に制限されないが、一般に1nm以上が、生産性の観点から好ましい。
なお、本明細書において、フィルターの細孔径とは、イソプロパノール(IPA)のバブルポイントによって決定される細孔径を意味する。 -Pore size of filter The pore size of the filter is not particularly limited, and a filter having a pore size usually used for filtering a substance to be purified can be used. Above all, the pore diameter of the filter is preferably 200 nm or less, more preferably 20 nm or less, still more preferably 10 nm or less, and more preferably 5 nm or less, in that the number of particles (metal particles and the like) contained in the drug solution can be easily controlled in a desired range. Is particularly preferred. The lower limit is not particularly limited, but is generally preferably 1 nm or more from the viewpoint of productivity.
In addition, in this specification, the pore diameter of a filter means the pore diameter determined by the bubble point of isopropanol (IPA).
なお、微小孔径フィルターは単独で用いてもよいし、他の細孔径を有するフィルターと使用してもよい。中でも、生産性により優れる観点から、より大きな細孔径を有するフィルターと使用するのが好ましい。つまり、2以上のフィルターを用いる場合、少なくとも1つのフィルターの細孔径が5.0nm以下であることが好ましい。この場合、予めより大きな細孔径を有するフィルターによってろ過した被精製物を、微小孔径フィルターに通液させれば、微小孔径フィルターの目詰まりを防げる。
すなわち、フィルターの細孔径としては、フィルターを1つ用いる場合には、細孔径は5.0nm以下が好ましく、フィルターを2つ以上用いる場合、最小の細孔径を有するフィルターの細孔径が5.0nm以下が好ましい。 It is preferable that the pore diameter of the filter be 5.0 nm or less, since the number of particles contained in the drug solution can be more easily controlled. Hereinafter, a filter having a pore size of 5.0 nm or less is also referred to as a “micropore size filter”.
The micropore size filter may be used alone, or may be used with a filter having another pore size. Among them, it is preferable to use a filter having a larger pore diameter from the viewpoint of better productivity. That is, when two or more filters are used, it is preferable that at least one filter has a pore diameter of 5.0 nm or less. In this case, if the object to be purified, which has been filtered through a filter having a larger pore diameter in advance, is passed through a micropore size filter, clogging of the micropore size filter can be prevented.
That is, when one filter is used, the pore diameter of the filter is preferably 5.0 nm or less, and when two or more filters are used, the pore diameter of the filter having the smallest pore diameter is 5.0 nm. The following is preferred.
フィルターの材料としては特に制限されず、フィルターの材料として公知の材料が使用できる。具体的には、樹脂である場合、ナイロン(例えば、6-ナイロン及び6,6-ナイロン)等のポリアミド;ポリエチレン、及び、ポリプロピレン等のポリオレフィン;ポリスチレン;ポリイミド;ポリアミドイミド;ポリ(メタ)アクリレート;ポリテトラフルオロエチレン、パーフルオロアルコキシアルカン、パーフルオロエチレンプロペンコポリマー、エチレン・テトラフルオロエチレンコポリマー、エチレン-クロロトリフロオロエチレンコポリマー、ポリクロロトリフルオロエチレン、ポリフッ化ビニリデン、及び、ポリフッ化ビニル等のポリフルオロカーボン;ポリビニルアルコール;ポリエステル;セルロース;セルロースアセテート等が挙げられる。
中でも、より優れた耐溶剤性を有し、得られる薬液がより優れた欠陥抑制性能を有する点で、ナイロン(中でも、6,6-ナイロンが好ましい)、ポリオレフィン(中でも、ポリエチレンが好ましい)、ポリ(メタ)アクリレート、及び、ポリフルオロカーボン(中でも、ポリテトラフルオロエチレン(PTFE)、パーフルオロアルコキシアルカン(PFA)が好ましい。)からなる群から選択される少なくとも1種が好ましい。これらの重合体は単独で又は2種以上を組み合わせて使用できる。
また、樹脂以外にも、ケイソウ土、及び、ガラス等であってもよい。
他にも、ポリオレフィン(後述するUPE(超高分子量ポリエチレン)等)にポリアミド(例えば、ナイロン-6又はナイロン-6,6等のナイロン)をグラフト共重合させたポリマー(ナイロングラフトUPE等)をフィルターの材料としてもよい。 -Material of the filter The material of the filter is not particularly limited, and known materials for the filter can be used. Specifically, when it is a resin, polyamide such as nylon (for example, 6-nylon and 6,6-nylon); polyolefin such as polyethylene and polypropylene; polystyrene; polyimide; polyamideimide; Polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylene propene copolymer, ethylene / tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride Fluorocarbon; polyvinyl alcohol; polyester; cellulose; cellulose acetate and the like.
Among them, nylon (especially, 6,6-nylon is preferred), polyolefin (especially, polyethylene is preferred), and polyolefin are preferred in that they have better solvent resistance and the resulting chemical has more excellent defect suppression performance. At least one selected from the group consisting of (meth) acrylate and polyfluorocarbon (among others, polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkane (PFA) is preferable) is preferable. These polymers can be used alone or in combination of two or more.
In addition to the resin, diatomaceous earth, glass, and the like may be used.
In addition, a polymer (eg, nylon grafted UPE) obtained by graft copolymerizing a polyamide (eg, nylon-6 or nylon-6,6, etc.) with a polyolefin (eg, UPE (ultra high molecular weight polyethylene) described below) is used as a filter. Material.
すなわち、フィルターとしては、イオン交換基を有するフィルターが好ましい。
イオン交換基としては、カチオン交換基及びアニオン交換基が挙げられ、カチオン交換基として、スルホン酸基、カルボキシ基、及び、リン酸基等が挙げられ、アニオン交換基として、4級アンモニウム基等が挙げられる。イオン交換基をフィルターに導入する方法としては特に制限されないが、イオン交換基と重合性基とを含有する化合物をフィルターと反応させ典型的にはグラフト化する方法が挙げられる。 As the chemical modification treatment, a method of introducing an ion exchange group into a filter is preferable.
That is, a filter having an ion exchange group is preferable as the filter.
Examples of the ion exchange group include a cation exchange group and an anion exchange group. Examples of the cation exchange group include a sulfonic acid group, a carboxy group, and a phosphate group, and examples of the anion exchange group include a quaternary ammonium group. No. The method for introducing the ion-exchange group into the filter is not particularly limited, and examples thereof include a method in which a compound containing an ion-exchange group and a polymerizable group is allowed to react with the filter and typically grafted.
イオン交換基を有するフィルターの細孔径は特に制限されないが、1~30nmが好ましく、5~20nmがより好ましい。イオン交換基を有するフィルターは、既に説明した最小の細孔径を有するフィルターを兼ねてもよいし、最小の細孔径を有するフィルターとは別に使用してもよい。中でも、より優れた本発明の効果を示す薬液が得られる点で、ろ過工程は、イオン交換基を有するフィルターと、イオン交換基を有さず、最小の細孔径を有するフィルターとを使用する形態が好ましい。
既に説明した最小の細孔径を有するフィルターの材料としては特に制限されないが、耐溶剤性等の観点から、一般に、ポリフルオロカーボン、及び、ポリオレフィンからなる群より選択される少なくとも1種が好ましく、ポリオレフィンがより好ましい。 When a filter having an ion exchange group is used, it is easy to control the contents of the metal-containing particles and metal ions in the chemical solution in a desired range. The material constituting the filter having an ion exchange group is not particularly limited, and examples thereof include a polyfluorocarbon and a material in which an ion exchange group is introduced into polyolefin, and a material in which an ion exchange group is introduced into polyfluorocarbon is more preferable.
Although the pore diameter of the filter having an ion exchange group is not particularly limited, it is preferably 1 to 30 nm, more preferably 5 to 20 nm. The filter having an ion-exchange group may also serve as the filter having the smallest pore diameter described above, or may be used separately from the filter having the smallest pore diameter. Above all, in the point that a drug solution exhibiting a superior effect of the present invention can be obtained, the filtration step uses a filter having an ion exchange group and a filter having no ion exchange group and having a minimum pore diameter. Is preferred.
The material of the filter having the smallest pore diameter already described is not particularly limited, but from the viewpoint of solvent resistance and the like, generally, polyfluorocarbon, and at least one selected from the group consisting of polyolefins are preferable. More preferred.
フィルターの細孔構造としては特に制限されず、被精製物中の成分に応じて適宜選択すればよい。本明細書において、フィルターの細孔構造とは、細孔径分布、フィルター中の細孔の位置的な分布、及び、細孔の形状等を意味し、典型的には、フィルターの製造方法により制御可能である。
例えば、樹脂等の粉末を焼結して形成すれば多孔質膜が得られ、エレクトロスピニング、エレクトロブローイング、及び、メルトブローイング等の方法により形成すれば繊維膜が得られる。これらは、それぞれ細孔構造が異なる。 -Pore structure of filter The pore structure of the filter is not particularly limited, and may be appropriately selected according to the components in the object to be purified. In the present specification, the pore structure of a filter means a pore size distribution, a positional distribution of pores in a filter, and a shape of pores, and is typically controlled by a filter manufacturing method. It is possible.
For example, a porous film can be obtained by sintering a powder of a resin or the like, and a fiber film can be obtained by forming by a method such as electrospinning, electroblowing, and meltblowing. These have different pore structures.
なお、本明細書で使用される「非ふるい」による保持機構は、フィルターの圧力降下、又は、細孔径に関連しない、妨害、拡散及び吸着等の機構によって生じる保持を指す。 If the object to be purified contains negatively charged particles, a polyamide filter acts as a non-sieving membrane to remove such particles. Typical non-sieving membranes include, but are not limited to, nylon-6 membranes and nylon membranes such as nylon-6,6 membranes.
As used herein, "non-sieving" retention mechanism refers to retention caused by mechanisms such as filter pressure drop or interference, diffusion, and adsorption that are not related to pore size.
ふるい膜の典型的な例としては、ポリテトラフルオロエチレン(PTFE)膜とUPE膜が含まれるが、これらに制限されない。
なお、「ふるい保持機構」とは、除去対象粒子が多孔質膜の細孔径よりも大きいことによる結果の保持を指す。ふるい保持力は、フィルターケーキ(膜の表面での除去対象となる粒子の凝集)を形成することによって向上させられる。フィルターケーキは、2次フィルターの機能を効果的に果たす。 UPE filters are typically sieved membranes. A sieve membrane means a membrane that mainly captures particles via a sieve holding mechanism, or a membrane that is optimized for capturing particles via a sieve holding mechanism.
Typical examples of sieving membranes include, but are not limited to, polytetrafluoroethylene (PTFE) membranes and UPE membranes.
Note that the “sieve holding mechanism” refers to holding the result due to the removal target particles being larger than the pore diameter of the porous membrane. The sieve retention is improved by forming a filter cake (agglomeration of the particles to be removed on the surface of the membrane). The filter cake effectively performs the function of a secondary filter.
多孔質膜における細孔の大きさの分布とその膜中における位置の分布は、特に制限されない。大きさの分布がより小さく、かつ、その膜中における分布位置が対称であってもよい。また、大きさの分布がより大きく、かつ、その膜中における分布位置が非対称であってもよい(上記の膜を「非対称多孔質膜」ともいう。)。非対称多孔質膜では、孔の大きさは膜中で変化し、典型的には、膜一方の表面から膜の他方の表面に向かって孔径が大きくなる。このとき、孔径の大きい細孔が多い側の表面を「オープン側」といい、孔径が小さい細孔が多い側の表面を「タイト側」ともいう。
また、非対称多孔質膜としては、例えば、細孔の大きさが膜の厚さ内のある位置においてで最小となる膜(これを「砂時計形状」ともいう。)が挙げられる。 The pore structure of the porous membrane (for example, a porous membrane containing UPE, PTFE, or the like) is not particularly limited, and examples of the pore shape include a lace shape, a string shape, and a node shape. Can be
The distribution of pore sizes in the porous membrane and the distribution of positions in the membrane are not particularly limited. The size distribution may be smaller and the distribution position in the film may be symmetric. Further, the size distribution may be larger and the distribution position in the film may be asymmetric (the above film is also referred to as “asymmetric porous film”). In an asymmetric porous membrane, the size of the pores varies in the membrane, and typically the pore size increases from one surface of the membrane to the other surface of the membrane. At this time, the surface on the side with many pores having a large pore diameter is called “open side”, and the surface on the side with many pores with small pore diameter is also called “tight side”.
Examples of the asymmetric porous membrane include a membrane in which the size of pores is minimized at a certain position within the thickness of the membrane (this is also referred to as an “hourglass shape”).
中でも、多孔質膜の材料としては、超高分子量ポリエチレンが好ましい。超高分子量ポリエチレンは、極めて長い鎖を有する熱可塑性ポリエチレンを意味し、分子量が百万以上、典型的には、200~600万が好ましい。 The porous membrane may include thermoplastic polymers such as PESU (polyethersulfone), PFA (perfluoroalkoxyalkane, copolymer of ethylene tetrafluoride and perfluoroalkoxyalkane), polyamide, and polyolefin. , Polytetrafluoroethylene and the like.
Among them, ultrahigh molecular weight polyethylene is preferable as the material of the porous membrane. Ultra-high molecular weight polyethylene means a thermoplastic polyethylene having an extremely long chain, and preferably has a molecular weight of 1,000,000 or more, typically 2,000,000 to 6,000,000.
未洗浄のフィルター(又は十分な洗浄がされていないフィルター)を使用する場合、フィルターが含有する不純物が薬液に持ち込まれやすい。 Further, it is preferable that the filter is sufficiently washed before use.
When an unwashed filter (or a filter that has not been sufficiently washed) is used, impurities contained in the filter are likely to be brought into the chemical solution.
また、同一のフィルターに被精製物を複数回通過させてもよく、同種のフィルターの複数に、被精製物を通過させてもよい。 As described above, in the filtration step according to the embodiment of the present invention, at least one selected from the group consisting of a filter material, a pore diameter, and a pore structure passes the material to be purified through two or more types of different filters. And a multi-stage filtration step.
The object to be purified may be passed through the same filter a plurality of times, or the object to be purified may be passed through a plurality of filters of the same type.
非金属材料としては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、ポリエチレン-ポリプロピレン樹脂、並びに、フッ素系樹脂(例えば、四フッ化エチレン樹脂、四フッ化エチレン-パーフルオロアルキルビニルエーテル共重合体、四フッ化エチレン-六フッ化プロピレン共重合樹脂、四フッ化エチレン-エチレン共重合体樹脂、三フッ化塩化エチレン-エチレン共重合樹脂、フッ化ビニリデン樹脂、三フッ化塩化エチレン共重合樹脂、及び、フッ化ビニル樹脂等)からなる群から選択される少なくとも1種が挙げられるが、これに制限されない。 The nonmetallic material is not particularly limited, and a known material can be used.
Examples of the non-metallic material include polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, and fluorine-based resin (eg, ethylene tetrafluoride resin, ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer, -Propylene hexafluoride copolymer resin, ethylene tetrafluoride-ethylene copolymer resin, ethylene trifluoride-ethylene copolymer resin, vinylidene fluoride resin, ethylene trifluoride ethylene copolymer resin, and vinyl fluoride At least one selected from the group consisting of resins and the like, but is not limited thereto.
金属材料としては、例えば、クロム及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%超である金属材料が挙げられ、中でも、30質量%以上がより好ましい。金属材料におけるクロム及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、一般に90質量%以下が好ましい。
金属材料としては例えば、ステンレス鋼、及びニッケル-クロム合金等が挙げられる。 The metal material is not particularly limited, and a known material can be used.
Examples of the metal material include a metal material in which the total content of chromium and nickel is more than 25% by mass based on the total mass of the metal material, and among them, 30% by mass or more is more preferable. The upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is generally preferably 90% by mass or less.
Examples of the metal material include stainless steel and a nickel-chromium alloy.
ニッケル-クロム合金としては、例えば、ハステロイ(商品名、以下同じ。)、モネル(商品名、以下同じ)、及び、インコネル(商品名、以下同じ)が挙げられる。より具体的には、ハステロイC-276(Ni含有量63質量%、Cr含有量16質量%)、ハステロイ-C(Ni含有量60質量%、Cr含有量17質量%)、及び、ハステロイC-22(Ni含有量61質量%、Cr含有量22質量%)が挙げられる。
また、ニッケル-クロム合金は、必要に応じて、上記した合金の他に、更に、ホウ素、ケイ素、タングステン、モリブデン、銅、及び、コバルト等を含有していてもよい。 The nickel-chromium alloy is not particularly limited, and a known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass is preferable.
Examples of the nickel-chromium alloy include Hastelloy (trade name, the same applies hereinafter), Monel (trade name, the same applies hereinafter), and Inconel (trade name, the same applies hereinafter). More specifically, Hastelloy C-276 (Ni content 63% by mass, Cr content 16% by mass), Hastelloy-C (Ni content 60% by mass, Cr content 17% by mass), and Hastelloy C-276 22 (Ni content 61% by mass, Cr content 22% by mass).
Further, the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt, and the like, if necessary, in addition to the above alloy.
なお、金属材料はバフ研磨されていてもよい。バフ研磨の方法は特に制限されず、公知の方法を使用できる。バフ研磨の仕上げに用いられる研磨砥粒のサイズは特に制限されないが、金属材料の表面の凹凸がより小さくなりやすい点で、#400以下が好ましい。なお、バフ研磨は、電解研磨の前に行われるのが好ましい。 It is presumed that the metal material has a higher chromium content in the passivation layer on the surface than a chromium content in the matrix due to electrolytic polishing. Therefore, it is presumed that the use of a refining device in which the liquid contact portion is formed from a metal material which has been electropolished, makes it difficult for metal-containing particles to flow out into the object to be purified.
The metal material may be buffed. The buffing method is not particularly limited, and a known method can be used. The size of the abrasive grains used for the buffing finish is not particularly limited, but is preferably # 400 or less from the viewpoint that irregularities on the surface of the metal material tend to be smaller. The buff polishing is preferably performed before the electrolytic polishing.
薬液の製造方法は、ろ過工程以外の工程を更に有していてもよい。ろ過工程以外の工程としては、例えば、蒸留工程、反応工程、及び、除電工程等が挙げられる。 (Other processes)
The method for producing a chemical solution may further include a step other than the filtration step. The steps other than the filtration step include, for example, a distillation step, a reaction step, and a charge removal step.
蒸留工程は、有機溶剤を含有する被精製物を蒸留して、蒸留済み被精製物を得る工程である。被精製物を蒸留する方法としては特に制限されず、公知の方法が使用できる。典型的には、ろ過工程に供される精製装置の一次側に、蒸留塔を配置し、蒸留された被精製物を製造タンクに導入する方法が挙げられる。
このとき、蒸留塔の接液部は特に制限されないが、既に説明した耐腐食材料で形成されるのが好ましい。 (Distillation process)
The distillation step is a step of distilling an object to be purified containing an organic solvent to obtain a distilled object to be purified. The method for distilling the object to be purified is not particularly limited, and a known method can be used. Typically, there is a method in which a distillation column is arranged on the primary side of a purification device provided for a filtration step, and a distilled product to be purified is introduced into a production tank.
At this time, the liquid contact portion of the distillation column is not particularly limited, but is preferably formed of the corrosion-resistant material described above.
反応工程は、原料を反応させて、反応物である有機溶剤を含有する被精製物を生成する工程である。被精製物を生成する方法としては特に制限されず、公知の方法が使用できる。典型的には、ろ過工程に供される精製装置の製造タンク(又は、蒸留塔)の一次側に反応槽を配置し、反応物を製造タンク(又は蒸留塔)に導入する方法が挙げられる。
このとき、製造タンクの接液部としては特に制限されないが、既に説明した耐腐食材料で形成されるのが好ましい。 (Reaction step)
The reaction step is a step of reacting the raw materials to produce a purified product containing an organic solvent as a reactant. The method for producing the object to be purified is not particularly limited, and a known method can be used. Typically, there is a method in which a reaction tank is arranged on the primary side of a production tank (or a distillation column) of a purification device provided for a filtration step, and a reactant is introduced into the production tank (or a distillation column).
At this time, the liquid contact portion of the production tank is not particularly limited, but is preferably formed of the corrosion-resistant material described above.
除電工程は、被精製物を除電して、被精製物の帯電電位を低減させる工程である。
除電方法としては特に制限されず、公知の除電方法を使用できる。除電方法としては、例えば、被精製物を導電性材料に接触させる方法が挙げられる。
被精製物を導電性材料に接触させる接触時間は、0.001~60秒が好ましく、0.001~1秒がより好ましく、0.01~0.1秒が更に好ましい。導電性材料としては、ステンレス鋼、金、白金、ダイヤモンド、及び、グラッシーカーボンが挙げられる。
被精製物を導電性材料に接触させる方法としては、例えば、導電性材料からなる接地されたメッシュを管路内部に配置し、ここに被精製物を通す方法等が挙げられる。 (Static elimination process)
The charge elimination step is a step of removing charges from the object to be purified to reduce the charged potential of the object to be purified.
The static elimination method is not particularly limited, and a known static elimination method can be used. Examples of the charge removal method include a method of contacting the object to be purified with a conductive material.
The contact time for contacting the object to be purified with the conductive material is preferably from 0.001 to 60 seconds, more preferably from 0.001 to 1 second, even more preferably from 0.01 to 0.1 second. Examples of the conductive material include stainless steel, gold, platinum, diamond, and glassy carbon.
As a method of bringing the object to be purified into contact with the conductive material, for example, a method of arranging a grounded mesh made of a conductive material in a pipe and passing the object through the pipe is mentioned.
上記精製方法により製造された薬液は、容器に収容されて使用時まで保管してもよい。
このような容器と、容器に収容された薬液とをあわせて薬液収容体という。保管された薬液収容体からは、薬液が取り出され使用される。 <Chemical container>
The drug solution produced by the above purification method may be stored in a container and stored until use.
A combination of such a container and a drug solution contained in the container is referred to as a drug solution container. The medicinal solution is taken out from the stored medicinal solution container and used.
使用可能な容器としては、具体的には、アイセロ化学(株)製の「クリーンボトル」シリーズ、及び、コダマ樹脂工業製の「ピュアボトル」等が挙げられるが、これらに制限されない。 As a container for storing the chemical solution, it is preferable that the container has a high degree of cleanness and a small amount of impurities eluted for use in semiconductor device manufacturing.
Specific examples of usable containers include, but are not limited to, “Clean Bottle” series manufactured by Aicello Chemical Co., Ltd. and “Pure Bottle” manufactured by Kodama Resin Kogyo.
なお、上記空隙率は、式(1)に従って計算される。
式(1):空隙率={1-(容器内の薬液の体積/容器の容器体積)}×100
上記容器体積とは、容器の内容積(容量)と同義である。
空隙率をこの範囲に設定することで、不純物等のコンタミを制限する事で保管安定性を確保できる。 The porosity of the liquid medicine container in the container is preferably 2 to 80% by volume, more preferably 2 to 50% by volume, and still more preferably 5 to 30% by volume.
Note that the porosity is calculated according to equation (1).
Formula (1): Porosity = {1− (volume of drug solution in container / volume of container)} × 100
The container volume is synonymous with the internal volume (capacity) of the container.
By setting the porosity in this range, storage stability can be ensured by limiting contamination such as impurities.
フィルターとしては、以下のフィルターを使用した。
・「Purasol SN 200nm」:UPEメンブレン(材質)、Entegris社製、孔径200nm
・「PP 200nm」:ポリプロピレン製フィルター、Entegris社製、孔径200nm
・「Purasol SP 200nm」:UPEメンブレン(材質)Entegris社製、孔径200nm
・「Octolex 5nm」:UPE製Nylonフィルターグラフト、Entegris社製、孔径5nm
・「IEX 15nm」:イオン交換樹脂フィルター、Entegris社製、孔径15nm
・「IEX 50nm」:イオン交換樹脂フィルター、Entegris社製、孔径50nm
・「IEX 200nm」:イオン交換樹脂フィルター、Entegris社製、孔径200nm
・「PTFE 5nm」:ポリテトラフルオロエチレン製フィルター、Entegris社製、孔径5nm
・「PTFE 7nm」:ポリテトラフルオロエチレン製フィルター、Entegris社製、孔径7nm
・「PTFE 10nm」:ポリテトラフルオロエチレン製フィルター、Entegris社製、孔径10nm
・「PTFE 20nm」:ポリテトラフルオロエチレン製フィルター、Entegris社製、孔径20nm
・「Nylon 5nm」:ナイロン製フィルター、Pall社製、孔径5nm
・「UPE 1nm」:超高分子量ポリエチレン製フィルター、Pall社製、孔径1nm
・「UPE 3nm」:超高分子量ポリエチレン製フィルター、Pall社製、孔径3nm
・「UPE 5nm」:超高分子量ポリエチレン製フィルター、Pall社製、孔径5nm (filter)
The following filters were used as filters.
-"Purasol SN 200 nm": UPE membrane (material), manufactured by Entegris, pore size 200 nm
"PP 200 nm": polypropylene filter, manufactured by Entegris, pore size 200 nm
-"Purasol SP 200 nm": UPE membrane (material) manufactured by Entegris, pore size 200 nm
-"Octolex 5 nm": Nylon filter graft made by UPE, manufactured by Entegris, pore size 5 nm
"IEX 15 nm": ion exchange resin filter, manufactured by Entegris, pore size 15 nm
"IEX 50 nm": ion exchange resin filter, manufactured by Entegris, pore size 50 nm
"IEX 200 nm": ion exchange resin filter, manufactured by Entegris, pore size 200 nm
-"PTFE 5 nm": Polytetrafluoroethylene filter, manufactured by Entegris, pore size 5 nm
-"PTFE 7 nm": polytetrafluoroethylene filter, manufactured by Entegris, pore size 7 nm
-"PTFE 10 nm": Polytetrafluoroethylene filter, manufactured by Entegris, pore size 10 nm
-"PTFE 20 nm": Polytetrafluoroethylene filter, manufactured by Entegris, pore size 20 nm
-"Nylon 5 nm": Nylon filter, manufactured by Pall, pore size 5 nm
-"UPE 1 nm": Ultra-high molecular weight polyethylene filter, manufactured by Pall, pore size 1 nm
-"UPE 3 nm": Ultra high molecular weight polyethylene filter, manufactured by Pall, pore size 3 nm
-"UPE 5 nm": Ultra high molecular weight polyethylene filter, manufactured by Pall, pore size 5 nm
実施例、及び、比較例の薬液の製造のために、以下の有機溶剤を被精製物として使用した。
・CyHe:シクロヘキサノン
・PGMEA:プロピレングリコールモノメチルエーテルアセテート
・MIBC:4-メチル-2-ペンタノール
・nBA:酢酸ブチル
・EL:乳酸エチル
・PC:炭酸プロピレン
・IPA:イソプロパノール
・PGMEE:プロピレングリコールモノエチルエーテル
・PGMPE:プロピレングリコールモノプロピルエーテル
・CPN:シクロペンタノン
また、表中の「原料1」~「原料19」は、各実施例及び比較例で用いた有機溶剤が以下のメーカーからの購入品であることを表す。
「原料1」:Honeywell
「原料2」:東洋合成
「原料3」:BASF
「原料4」:宇部興産
「原料5」:KHネオケム
「原料6」:昭和電工
「原料7」:KMG Electronic Chemical
「原料8」:WAKO
「原料9」:KHネオケム
「原料10」:三和油化工業
「原料11」:Shell Groval
「原料12」:関東化学
「原料13」:林純薬
「原料14」:CCP
「原料15」:BASF
「原料16」:ENF
「原料17」:Shiny
「原料18」:KHネオケム
「原料19」:林純薬 <Substance to be purified>
The following organic solvents were used as substances to be purified for the production of the chemical solutions of the examples and comparative examples.
• CyHe: cyclohexanone • PGMEA: propylene glycol monomethyl ether acetate • MIBC: 4-methyl-2-pentanol • nBA: butyl acetate • EL: ethyl lactate • PC: propylene carbonate • IPA: isopropanol • PGMEE: propylene glycol monoethyl ether・ PGMPE: Propylene glycol monopropyl ether ・ CPN: Cyclopentanone The “raw materials 1” to “raw materials 19” in the table are organic solvents used in the respective Examples and Comparative Examples purchased from the following manufacturers. Indicates that there is.
"Raw material 1": Honeywell
"Raw material 2": Toyo Gosei "Raw material 3": BASF
"Raw material 4": Ube Industries "Raw material 5": KH Neochem "Raw material 6": Showa Denko "Raw material 7": KMG Electronic Chemical
"Raw material 8": WAKO
"Raw material 9": KH Neochem "Raw material 10": Sanwa Yuka Kogyo "Raw material 11": Shell Global
"Raw material 12": Kanto Chemical "Raw material 13": Hayashi Junyaku "Raw material 14": CCP
"Raw material 15": BASF
"Raw material 16": ENF
"Raw material 17": Shiny
"Raw material 18": KH Neochem "Raw material 19": Hayashi Junyaku
薬液を収納する容器としては、下記容器を使用した。
・EP-SUS:接液部が電解研磨されたステンレス鋼である容器 <Container>
The following containers were used as containers for storing the chemicals.
・ EP-SUS: A container whose wetted part is made of electropolished stainless steel
上記被精製物から選択した1種を選択し、表1に記載の蒸留精製処理を行った。
なお、表中の「蒸留精製」欄の「有-1」は蒸留塔(理論段数:15段)を用いた常圧蒸留を実施したことを表し、「有-2」は蒸留塔(理論段数:25段)を用いた減圧蒸留を実施したことを表し、「有-3」は蒸留塔(理論段数:30段)を用いた減圧蒸留を2回実施したことを表し、「有-4」は蒸留塔(理論段数:20段)を用いた常圧蒸留を実施したことを表し、「有-5」は蒸留塔(理論段数:10段)を用いた常圧蒸留を実施したことを表し、「有-6」は蒸留塔(理論段数:8段)を用いた常圧蒸留を実施したことを表す。
ただし、表中の「蒸留精製」欄の「無」は蒸留処理を実施していないことを表し、「蒸留精製」欄が「無」である例においては、蒸留精製を行っていない。 <Purification procedure>
One selected from the above-mentioned purified products was subjected to the distillation purification treatment shown in Table 1.
In the table, “Yes-1” in the column “Distillation purification” indicates that atmospheric distillation was performed using a distillation column (the number of theoretical plates: 15), and “Yes-2” indicates a distillation column (the number of theoretical plates). : 25 stages), and “Yes-3” means that vacuum distillation was performed twice using a distillation column (theoretical plate number: 30 stages), and “Yes-4”. Indicates that atmospheric distillation was performed using a distillation column (theoretical plate number: 20), and “Yes-5” indicates that atmospheric distillation was performed using a distillation column (theoretical plate number: 10). , "Yes-6" means that atmospheric distillation was performed using a distillation column (the number of theoretical plates: 8).
However, “none” in the “distillation purification” column in the table indicates that the distillation treatment was not performed, and in the example in which the “distillation purification” column is “none”, no distillation purification was performed.
次に、貯蔵タンクに貯蔵された被精製物を、表1に記載のフィルター6~7でろ過して、フィルター7でろ過した後の被精製物をフィルター6の上流側に循環し、再度フィルター6~7でろ過する循環ろ過処理を実施した。
循環ろ過処理の後、容器に薬液を収容した。
なお、実施例113~116に関しては、水分量が所定の値となるように、薬液中に水を添加した。 Next, the purified product purified by distillation is stored in a storage tank, and the purified product stored in the storage tank is passed through filters 1 to 5 shown in Table 1 in this order and filtered. Stored in tank.
Next, the object to be purified stored in the storage tank is filtered through the filters 6 to 7 shown in Table 1, and the object to be purified after being filtered through the filter 7 is circulated upstream of the filter 6, and then filtered again. A circulating filtration process of filtering at 6 to 7 was performed.
After the circulation filtration treatment, the drug solution was stored in the container.
In Examples 113 to 116, water was added to the chemical so that the water content became a predetermined value.
薬液中の金属成分(金属イオン、金属含有粒子)の含有量は、ICP-MS及びSP-ICP-MSを用いる方法により測定した。
装置は以下の装置を使用した。
・メーカー:PerkinElmer
・型式:NexION350S
解析には以下の解析ソフトを使用した。
・“SP-ICP-MS”専用Syngistix ナノアプリケーションモジュール
・Syngistix for ICP-MS ソフトウェア
但し、10nm以下の金属含有粒子はSP-ICP-MSでは測定できないため、上述した特定方法を用いた。 <Content of metal component>
The content of metal components (metal ions, metal-containing particles) in the chemical solution was measured by a method using ICP-MS and SP-ICP-MS.
The following equipment was used.
・ Manufacturer: PerkinElmer
・ Model: NexION350S
The following analysis software was used for the analysis.
・ Syngisix nano application module dedicated to “SP-ICP-MS” ・ Syngisix for ICP-MS software However, since the metal-containing particles of 10 nm or less cannot be measured by SP-ICP-MS, the above-mentioned specific method was used.
各種薬液における有機不純物の含有量は、ガスクロマトグラフィー質量分析(GC/MS)装置(Agilent社製、GC:7890B、MS:5977B EI/CI MSD)を使用して解析した。 <Content of organic impurities>
The content of organic impurities in various chemical solutions was analyzed using a gas chromatography mass spectrometer (GC / MS) (manufactured by Agilent, GC: 7890B, MS: 5977B EI / CI MSD).
〔プリウェット液又はリンス液〕
以下に示す方法で、製造した薬液の、プリウェット液又はリンス液として使用した場合の欠陥抑制性を評価した。
まず、直径300mmのシリコン基板、又は、直径300mmの酸化ケイ素膜付きシリコン基板(酸化ケイ素膜で表面が覆われたシリコン基板)に薬液をスピン吐出し、基板を回転させながら、基板の表面に対して、各薬液を0.5cc吐出した。その後、基板をスピン乾燥した。次に、KLA-Tencor社製のウエハ検査装置「SP-5」を用いて、薬液塗布後の基板に存在する欠陥数を計測した(これを計測値とする)。
次に、EDAX(energy-dispersive X-ray spectroscopy)を用いて、欠陥の種類を、金属残渣欠陥、複合物残渣欠陥、及び、シミ状残渣欠陥に分類した。金属残渣欠陥とは金属成分由来の残渣であり、複合物残渣欠陥とは有機物と金属成分との複合体由来の残渣であり、シミ状残渣欠陥とは有機物由来の残渣である。
なお、「Si上での金属残渣欠陥」が「D」以上であれば、プリウェット液又はリンス液として好適に用いられる。 <Test>
(Pre-wet liquid or rinse liquid)
By the method described below, the defect suppression property of the manufactured chemical solution when used as a pre-wet solution or a rinse solution was evaluated.
First, a chemical solution is spin-discharged onto a silicon substrate having a diameter of 300 mm or a silicon substrate having a silicon oxide film having a diameter of 300 mm (a silicon substrate whose surface is covered with a silicon oxide film). Then, 0.5 cc of each chemical solution was discharged. Thereafter, the substrate was spin-dried. Next, using a wafer inspection apparatus “SP-5” manufactured by KLA-Tencor, the number of defects present on the substrate after the application of the chemical was measured (this is referred to as a measured value).
Next, using EDAX (energy-dispersive X-ray spectroscopy), the types of defects were classified into metal residue defects, composite residue defects, and spot residue defects. The metal residue defect is a residue derived from a metal component, the composite residue defect is a residue derived from a composite of an organic substance and a metal component, and the stain residue defect is a residue derived from an organic substance.
If the “metal residue defect on Si” is “D” or more, it is suitably used as a pre-wet liquid or a rinsing liquid.
A:対応する欠陥数が20個/基板以下だった。
B:対応する欠陥数が20個/基板を超え、50個/基板以下だった。
C:対応する欠陥数が50個/基板を超え、100個/基板以下だった。
D:対応する欠陥数が100個/基板を超え、150個/基板以下だった。
E:対応する欠陥数が150個/基板を超えた。 <Individual evaluation (metal residue defect, composite residue defect, spot residue defect)>
A: The number of corresponding defects was 20 / substrate or less.
B: The number of corresponding defects exceeded 20 / substrate and was 50 / substrate or less.
C: The number of corresponding defects exceeded 50 / substrate and was 100 / substrate or less.
D: The number of corresponding defects exceeded 100 / substrate and was 150 / substrate or less.
E: The number of corresponding defects exceeded 150 / substrate.
以下に示す方法で、製造した薬液の、現像液として使用した場合を評価した。
まず、以下に示す操作によりレジストパターンを形成した。
直径300mmのシリコン基板、又は、直径300mmの酸化ケイ素膜付きシリコン基板に後述する感活性光線性又は感放射線性樹脂組成物を塗布し、100℃で、60秒間に亘ってプリベーク(PB)を行い、膜厚150nmのレジスト膜を形成した。 (Developer)
The following method was used to evaluate the case where the manufactured chemical was used as a developer.
First, a resist pattern was formed by the following operation.
An actinic ray-sensitive or radiation-sensitive resin composition described below is applied to a silicon substrate having a diameter of 300 mm or a silicon substrate having a silicon oxide film having a diameter of 300 mm, and prebaked (PB) at 100 ° C. for 60 seconds. A resist film having a thickness of 150 nm was formed.
酸分解性樹脂(下記式で表される樹脂(重量平均分子量(Mw):7500):各繰り返し単位に記載される数値はモル%を意味する。):100質量部 (Actinic ray-sensitive or radiation-sensitive resin composition)
Acid-decomposable resin (resin represented by the following formula (weight average molecular weight (Mw): 7500): the numerical value described in each repeating unit means mol%): 100 parts by mass
PGMEA(プロピレングリコールモノメチルエーテルアセテート):3質量部
シクロヘキサノン:600質量部
γ-BL(γ-ブチロラクトン):100質量部 solvent:
PGMEA (propylene glycol monomethyl ether acetate): 3 parts by mass Cyclohexanone: 600 parts by mass γ-BL (γ-butyrolactone): 100 parts by mass
得られたサンプルのスペース部において、上述した金属残渣欠陥、複合物残渣欠陥、及び、シミ状残渣欠陥の有無を上記方法に従って、評価した。 The wafer on which the resist film was formed was subjected to pattern exposure at 25 mJ / cm 2 using an ArF excimer laser scanner (Numerical Aperture: 0.75). Then, it heated at 120 degreeC for 60 second. Subsequently, each developing solution (chemical solution) was developed by paddle for 30 seconds. Next, the wafer was rotated at 4000 rpm for 30 seconds to form a negative resist pattern. Then, the obtained negative resist pattern was heated at 200 ° C. for 300 seconds. Through the above steps, an L / S pattern (average pattern width: 45 nm) having a line / space ratio of 1: 1 was obtained.
In the space portion of the obtained sample, the presence or absence of the above-described metal residue defect, composite residue defect, and spot-like residue defect was evaluated according to the above method.
表1中、「用途」欄の「用途1」は、各実施例及び比較例に記載の薬液をプリウェット液及びリンス液として用いて上記試験を実施したことを意味する。「用途」欄の「用途2」は、各実施例及び比較例に記載の薬液を現像液として用いて上記試験を実施したことを意味する。
なお、表中、「Si上での金属残渣」では、シリコン基板上での金属残渣欠陥の評価結果を示し、「Si上での複合物残渣」では、シリコン基板上での複合物残渣欠陥の評価結果を示し、「Si上でのシミ状残渣」では、シリコン基板上でのシミ状残渣欠陥の評価結果を示し、「SiO2上での金属残渣」では、酸化ケイ素膜付きシリコン基板上での金属残渣欠陥の評価結果を示し、「SiO2上での複合物残渣」では、酸化ケイ素膜付きシリコン基板上での複合物残渣欠陥の評価結果を示す。 In each example, the difference in pressure between the filters was 0.01 to 0.03 MPa.
In Table 1, "Usage 1" in the "Usage" column means that the above test was carried out using the chemical solutions described in each of Examples and Comparative Examples as a pre-wet liquid and a rinsing liquid. “Use 2” in the “use” column means that the above test was performed using the chemicals described in each of the examples and comparative examples as a developer.
In the table, “metal residue on Si” indicates the evaluation result of metal residue defect on the silicon substrate, and “composite residue on Si” indicates the result of composite residue defect on the silicon substrate. shows the evaluation results, the "stain-like residue on Si", shows the evaluation results of the stain-like residue defects on the silicon substrate, the "metal residue on SiO 2", a silicon oxide film-silicon substrate Shows the evaluation results of the metal residue defect, and “Composite residue on SiO 2 ” shows the evaluation result of the composite residue defect on the silicon substrate provided with the silicon oxide film.
また、表1中、「E+数字」は「10数字」を表し、例えば、「3.5E+04」は「3.5×104」を表す。
表1中、「<1」は、1未満を表す。
表1中、「<500ppb」は、500質量ppb未満を表す。 In Table 1, the “Ag ion amount (mass ppt)” column represents the silver ion content (mass ppt) with respect to the total mass of the chemical solution. The “metal component (mass ppt)” column indicates the content (mass ppt) of the metal component with respect to the total mass of the chemical solution. The column “Ag oxide particles / Ag ion” indicates a mass ratio of the content of silver oxide particles to the content of silver ions of 1. The “Pt ion amount (mass ppt)” column indicates the platinum ion content (mass ppt) with respect to the total mass of the chemical solution. The “Au ion amount (mass ppt)” column indicates the content (mass ppt) of gold ions with respect to the total mass of the chemical solution. The “number of Ti oxide particles” column indicates the number of titanium oxide particles in the chemical solution. The column “Ti oxide particles / Ag oxide particles” indicates the ratio of the content of titanium oxide particles to the content of silver oxide particles. The column “Ratio of Ag oxide particles (% by mass)” indicates the content (% by mass) of silver oxide particles with respect to the content of the silver component in the metal component. The column “Ratio of Ti oxide particles (% by mass)” indicates the content (% by mass) of the titanium oxide particles with respect to the content of the titanium component in the metal component. The column “Cu oxide particles / Cu ions” indicates the mass ratio of the content of Cu oxide particles to the content of Cu ions. The column “Fe oxide particles / Fe ions” indicates the mass ratio of the content of Fe oxide particles to the content of Fe ions. The column “Ratio of 0.5 to 17 nm Ti oxide particles (% by mass)” indicates the ratio (% by mass) of the titanium oxide particles having a particle size of 0.5 to 17 nm. The “moisture content” column indicates the water content (mass ppb) in the drug solution with respect to the total weight of the drug solution.
In Table 1, “E + number” represents “10 numbers ”, for example, “3.5E + 04” represents “3.5 × 10 4 ”.
In Table 1, “<1” represents less than 1.
In Table 1, "<500 ppb" represents less than 500 mass ppb.
例えば、実施例1においては、表1[その1]<1>に示すように、有機溶剤としてCyHeを用いて、表1[その1]<2>に示すように、フィルター2は「IEX 15nm」であり、表1[その1]<3>に示すように、薬液中のAgイオン量が0.8質量pptであり、表1[その1]<4>に示すように、酸化Ti粒子の数が2.1E+04であり、表1[その1]<5>に示すように、「酸化Fe粒子/Feイオン」の数が8.7E+4であり、表1[その1]<6>に示すように、「Si上での金属残渣」評価が「A」である。その他の実施例、及び、比較例についても同様である。 In Table 1, the data relating to each of the examples and the comparative examples are shown in Table 1 [Part 1] <1> to <6>, Table 1 [Part 2] <1> to <6>, Table 1 [Part 3] <1> to <6>, Table 1 [part 4] <1> to <6>, and Table 1 [part 5] <1> to <6>.
For example, in Example 1, as shown in Table 1 [Part 1] <1>, CyHe was used as the organic solvent, and as shown in Table 1 [Part 1] <2>, the filter 2 was “IEX 15 nm”. As shown in Table 1 [Part 1] <3>, the amount of Ag ions in the chemical solution is 0.8 mass ppt, and as shown in Table 1 [Part 1] <4>, Is 2.1E + 04, and as shown in Table 1 [Part 1] <5>, the number of “Fe oxide particles / Fe ions” is 8.7E + 4, and Table 1 [Part 1] <6> As shown, the “metal residue on Si” evaluation is “A”. The same applies to other examples and comparative examples.
特に、実施例1~7(実施例29~35、実施例57~63、実施例85~91)の比較より、銀イオンの含有量が、薬液全質量に対して、0.0020~0.90質量pptである場合、より効果が優れることが確認された。
また、実施例8~13(実施例36~41、実施例64~69、実施例92~97)の比較より、金属成分の含有量が、薬液全質量に対して、10.0~500質量pptである場合、より効果が優れることが確認された。
また、実施例14~18(実施例42~46、実施例70~74、実施例98~102)の比較より、銀イオンの含有量に対する、酸化銀粒子の含有量の質量比1が、0.00000010~0.1である場合、より効果が優れることが確認された。
また、実施例4~7(実施例32~35、実施例60~63、実施例88~91)の比較より、白金イオン又は金イオンの含有量が、薬液全質量に対して、0.000010~1.0質量pptである場合、より効果が優れることが確認された。
また、実施例19~22(実施例47~50、実施例75~78、実施例103~106)の比較より、酸化チタン粒子の数が、102~1010個である場合、より効果が優れることが確認された。
また、実施例23~26(実施例51~54、実施例79~82、実施例107~110)の比較より、酸化銀粒子の含有量に対する、酸化チタン粒子の含有量の比が102~1010である場合、より効果が優れることが確認された。
また、実施例14~18(実施例42~46、実施例70~74、実施例98~102)の比較より、酸化銀粒子の含有量が、金属成分中の銀成分の含有量に対して、0.00010~5.0質量%である場合、より効果が優れることが確認された。
また、実施例14~18(実施例42~46、実施例70~74、実施例98~102)の比較より、酸化チタン粒子の含有量が、金属成分中のチタン成分の含有量に対して、5質量%以上98質量%未満である場合、より効果が優れることが確認された。
また、実施例23~26(実施例51~54、実施例79~82、実施例107~110)の比較より、酸化チタン粒子のうち、粒径0.5~17nmである粒子の割合が、40質量%以上99質量%未満である場合、より効果が優れることが確認された。
また、実施例27及び28(55及び56、83及び84、111及び112)より、有機不純物の含有量が、薬液全質量に対して、1000~100000質量pptである場合、より効果が優れることが確認された。
また、実施例1及び2より、水分量が500体積ppb以下の場合、より効果が優れることが確認された。 From the results shown in the table, it was confirmed that the medicinal solution of the present invention could provide a predetermined effect.
In particular, from the comparison of Examples 1 to 7 (Examples 29 to 35, Examples 57 to 63, and Examples 85 to 91), the content of silver ions is 0.0020 to 0.2% with respect to the total mass of the chemical solution. When it was 90 mass ppt, it was confirmed that the effect was more excellent.
From the comparison of Examples 8 to 13 (Examples 36 to 41, Examples 64 to 69, and Examples 92 to 97), the content of the metal component was 10.0 to 500% by mass with respect to the total mass of the chemical solution. In the case of ppt, it was confirmed that the effect was more excellent.
Further, from the comparison of Examples 14 to 18 (Examples 42 to 46, Examples 70 to 74, and Examples 98 to 102), the mass ratio 1 of the content of silver oxide particles to the content of silver ions is 0. It was confirmed that the effect was more excellent when the value was 0.000000010 to 0.1.
Also, from the comparison of Examples 4 to 7 (Examples 32 to 35, Examples 60 to 63, and Examples 88 to 91), the content of platinum ions or gold ions was 0.000010 relative to the total mass of the chemical solution. It was confirmed that the effect was more excellent when it was 1.0 mass ppt.
In addition, according to comparison of Examples 19 to 22 (Examples 47 to 50, Examples 75 to 78, and Examples 103 to 106), when the number of titanium oxide particles is 10 2 to 10 10 , the effect is more improved. It was confirmed that it was excellent.
From the comparison of Examples 23 to 26 (Examples 51 to 54, Examples 79 to 82, and Examples 107 to 110), the ratio of the content of the titanium oxide particles to the content of the silver oxide particles was 10 2 to When it was 10 10 , it was confirmed that the effect was more excellent.
Also, from the comparison of Examples 14 to 18 (Examples 42 to 46, Examples 70 to 74, and Examples 98 to 102), the content of the silver oxide particles was more than the content of the silver component in the metal component. , 0.00010 to 5.0% by mass, it was confirmed that the effect was more excellent.
Also, from the comparison of Examples 14 to 18 (Examples 42 to 46, Examples 70 to 74, and Examples 98 to 102), the content of the titanium oxide particles was found to be higher than the content of the titanium component in the metal component. When the content was 5% by mass or more and less than 98% by mass, it was confirmed that the effect was more excellent.
From the comparison of Examples 23 to 26 (Examples 51 to 54, Examples 79 to 82, and Examples 107 to 110), the proportion of the titanium oxide particles having a particle size of 0.5 to 17 nm was found to be: When the content was 40% by mass or more and less than 99% by mass, it was confirmed that the effect was more excellent.
In addition, according to Examples 27 and 28 (55 and 56, 83 and 84, 111 and 112), the effect is more excellent when the content of organic impurities is 1,000 to 100,000 mass ppt with respect to the total mass of the chemical solution. Was confirmed.
Further, from Examples 1 and 2, it was confirmed that the effect was more excellent when the water content was 500 vol ppb or less.
また、実施例40の薬液(100L)を用いて、容器(EP-SUS)及び<精製手順>で使用する各種装置を洗浄した後、別途用意した実施例29の薬液を上記洗浄した装置に流して、洗浄した容器に回収して、容器中に溶液Bを得た。
溶液A及び溶液Bを用いて「Si上での金属残渣欠陥」の評価を行ったところ、溶液Aのほうが良好な結果が得られた。 After cleaning the container (EP-SUS) and various devices used in <Purification procedure> using the chemical solution (100 L) of Example 29, the separately prepared chemical solution of Example 29 was flowed into the above-described washed device, The solution was collected in a washed container, and a solution A was obtained in the container.
After cleaning the container (EP-SUS) and various devices used in <Purification Procedure> using the chemical solution (100 L) of Example 40, the chemical solution of Example 29 prepared separately was poured into the washed device. Then, the solution was collected in a washed container, and a solution B was obtained in the container.
When “metal residue defects on Si” was evaluated using solution A and solution B, better results were obtained with solution A.
まず、レジスト組成物1を、各成分を以下の組成で混合して得た。
・樹脂(A-1):0.77g
・光酸発生剤(B-1):0.03g
・塩基性化合物(E-3):0.03g
・PGMEA(市販品、高純度グレード):67.5g
・乳酸エチル(市販品、高純度グレード):75g <Example (EUV exposure)>
First, a resist composition 1 was obtained by mixing each component with the following composition.
・ Resin (A-1): 0.77 g
-Photoacid generator (B-1): 0.03 g
-Basic compound (E-3): 0.03 g
PGMEA (commercially available, high purity grade): 67.5 g
・ Ethyl lactate (commercially available, high purity grade): 75 g
樹脂(A-1)としては、以下の樹脂を用いた。 ・ Resin (A-1)
The following resin was used as the resin (A-1).
光酸発生剤(B-1)としては、以下の化合物を用いた。 .Photoacid generator (B-1)
The following compounds were used as the photoacid generator (B-1).
塩基性化合物(E-3)としては、以下の化合物を用いた。 .Basic compound (E-3)
The following compounds were used as the basic compound (E-3).
まず、直径300mmのシリコンウェハ上にレジスト組成物1を塗布し、100℃で60秒間ベーク(PB:Prebake)を行い、膜厚30nmのレジスト膜を形成した。 (Pattern formation and evaluation)
First, the resist composition 1 was applied on a silicon wafer having a diameter of 300 mm, and baked (PB: Prebake) at 100 ° C. for 60 seconds to form a resist film having a thickness of 30 nm.
上記リンス液としては、上述した実施例80で使用した薬液を用いた。なお、上述した、各種評価を実施したところ、表1と同様の傾向の所望の効果が得られた。
The resist film was exposed through a reflective mask using an EUV exposure machine (manufactured by ASML; NXE3350, NA 0.33, Dipole 90 °, outer sigma 0.87, inner sigma 0.35). Thereafter, heating (PEB: Post Exposure Bake) was performed at 85 ° C. for 60 seconds. Next, a developing solution (butyl acetate / manufactured by FETW) was sprayed for 30 seconds by a spray method for development, and a rinsing liquid was discharged onto a silicon wafer for 20 seconds by a spin coating method to be rinsed. Subsequently, the silicon wafer was rotated at a rotation speed of 2000 rpm for 40 seconds to form a line-and-space pattern having a space width of 20 nm and a pattern line width of 15 nm.
As the rinsing liquid, the chemical used in Example 80 described above was used. When the above-described various evaluations were performed, desired effects having the same tendency as in Table 1 were obtained.
Claims (17)
- 有機溶剤と金属成分とを含有する薬液であって、
前記金属成分が、銀イオンを含有し、
前記銀イオンの含有量が、前記薬液全質量に対して、0.0010~1.0質量pptである、薬液。 A chemical solution containing an organic solvent and a metal component,
The metal component contains silver ions,
The chemical solution, wherein the content of the silver ions is 0.0010 to 1.0 mass ppt with respect to the total mass of the chemical solution. - 前記金属成分の含有量が、前記薬液全質量に対して、10.0~500質量pptである、請求項1に記載の薬液。 薬 The chemical solution according to claim 1, wherein the content of the metal component is 10.0 to 500 mass ppt based on the total mass of the chemical solution.
- 前記金属成分が酸化銀粒子を含有し、
前記銀イオンの含有量に対する、前記酸化銀粒子の含有量の質量比1が、0.00000010~0.1である、請求項2に記載の薬液。 The metal component contains silver oxide particles,
3. The chemical solution according to claim 2, wherein the mass ratio 1 of the content of the silver oxide particles to the content of the silver ions is 0.00000010 to 0.1. - 前記酸化銀粒子の含有量が、前記金属成分中の銀成分の含有量に対して、0.00010~5.0質量%である、請求項3に記載の薬液。 4. The chemical solution according to claim 3, wherein the content of the silver oxide particles is 0.00010 to 5.0% by mass based on the content of the silver component in the metal component.
- 前記金属成分が、酸化チタン粒子、及び、チタンイオンを含有し、
前記チタンイオンの含有量に対する、前記酸化チタン粒子の含有量の質量比2と、前記質量比1とが以下の式(A)の関係を満たす、請求項3又は4に記載の薬液。
式(A) 質量比2>質量比1 The metal component contains titanium oxide particles, and titanium ions,
The chemical solution according to claim 3, wherein the mass ratio of the content of the titanium oxide particles to the content of the titanium ions and the mass ratio satisfy a relationship represented by the following formula (A).
Formula (A) Mass ratio 2> Mass ratio 1 - 前記酸化銀粒子の含有量に対する、前記酸化チタン粒子の含有量の比が102~1010である、請求項5に記載の薬液。 The chemical solution according to claim 5, wherein a ratio of a content of the titanium oxide particles to a content of the silver oxide particles is 10 2 to 10 10 .
- 前記酸化チタン粒子の数が、102~1010個である、請求項5又は6に記載の薬液。 The chemical solution according to claim 5, wherein the number of the titanium oxide particles is 10 2 to 10 10 .
- 前記酸化チタン粒子の含有量が、前記金属成分中のチタン成分の含有量に対して、5質量%以上98質量%未満である、請求項5~7のいずれか1項に記載の薬液。 8. The chemical solution according to claim 5, wherein the content of the titanium oxide particles is 5% by mass or more and less than 98% by mass with respect to the content of the titanium component in the metal component.
- 前記酸化チタン粒子のうち、粒径0.5~17nmである粒子の割合が、40質量%以上99質量%未満である、請求項5~8のいずれか1項に記載の薬液。 The chemical solution according to any one of claims 5 to 8, wherein the proportion of the titanium oxide particles having a particle size of 0.5 to 17 nm is 40% by mass or more and less than 99% by mass.
- 前記金属成分が、酸化銅粒子、及び、銅イオンを含有し、
前記銅イオンの含有量に対する、前記酸化銅粒子の含有量の質量比3と、前記質量比1とが以下の式(B)の関係を満たす、請求項3~9のいずれか1項に記載の薬液。
式(B) 質量比3>質量比1 The metal component contains copper oxide particles, and copper ions,
10. The mass spectrometer according to claim 3, wherein the mass ratio of the content of the copper oxide particles to the content of the copper ions is 3 and the mass ratio is 1 satisfies a relationship represented by the following formula (B). Liquid medicine.
Formula (B) Mass ratio 3> Mass ratio 1 - 前記金属成分が、酸化鉄粒子、及び、鉄イオンを含有し、
前記鉄イオンの含有量に対する、前記酸化鉄粒子の含有量の質量比4と、前記質量比1とが以下の式(C)の関係を満たす、請求項3~9のいずれか1項に記載の薬液。
式(C) 質量比4>質量比1 The metal component contains iron oxide particles, and iron ions,
10. The method according to claim 3, wherein a mass ratio of the content of the iron oxide particles to the iron ion content of 4 and the mass ratio of 1 satisfy a relationship represented by the following formula (C). Liquid medicine.
Formula (C) Mass ratio 4> Mass ratio 1 - 前記金属成分が、白金イオンを含有し、
前記白金イオンの含有量が、前記薬液全質量に対して、0.000010~1.0質量pptである、請求項1~11のいずれか1項に記載の薬液。 The metal component contains a platinum ion,
12. The chemical solution according to claim 1, wherein the content of the platinum ion is 0.000010 to 1.0 mass ppt based on the total mass of the chemical solution. - 前記金属成分が、金イオンを含有し、
前記金イオンの含有量が、前記薬液全質量に対して、0.000010~1.0質量pptである、請求項1~12のいずれか1項に記載の薬液。 The metal component contains a gold ion,
13. The chemical solution according to claim 1, wherein the content of the gold ion is 0.000010 to 1.0 mass ppt based on the total mass of the chemical solution. - 更に、有機不純物を含有し、
前記有機不純物の含有量が、前記薬液全質量に対して、1000~100000質量pptである、請求項1~13のいずれか1項に記載の薬液。 In addition, it contains organic impurities,
14. The chemical solution according to claim 1, wherein the content of the organic impurities is 1,000 to 100,000 mass ppt based on the total mass of the chemical solution. - 前記薬液全質量に対する水の含有量が500質量ppb以下である、請求項1~14のいずれか1項に記載の薬液。 The chemical according to any one of claims 1 to 14, wherein the content of water with respect to the total mass of the chemical is 500 mass ppb or less.
- 前記有機溶剤が、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、シクロヘキサノン、乳酸エチル、炭酸プロピレン、イソプロパノール、4-メチル-2-ペンタノール、酢酸ブチル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、メトキシプロピオン酸メチル、シクロペンタノン、γ-ブチロラクトン、ジイソアミルエーテル、酢酸イソアミル、ジメチルスルホキシド、N-メチルピロリドン、ジエチレングリコール、エチレングリコール、ジプロピレングリコール、プロピレングリコール、炭酸エチレン、スルフォラン、シクロヘプタノン、2-ヘプタノン、酪酸ブチル、イソ酪酸イソブチル、イソアミルエーテル、及び、ウンデカンからなる群から選ばれる1種以上を含む、請求項1~15のいずれか1項に記載の薬液。 The organic solvent is propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, propylene carbonate, isopropanol, 4-methyl-2-pentanol, butyl acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, Methyl methoxypropionate, cyclopentanone, γ-butyrolactone, diisoamyl ether, isoamyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cycloheptanone, 2 -From heptanone, butyl butyrate, isobutyl isobutyrate, isoamyl ether and undecane That contains at least one element selected from the group drug solution according to any one of claims 1 to 15.
- 容器と、前記容器に収容された請求項1~16のいずれか1項に記載の薬液と、を含有する、薬液収容体。 薬 A drug solution container comprising a container and the drug solution according to any one of claims 1 to 16 stored in the container.
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