WO2024163697A2 - Combined slurry copper waste and concentrated copper waste for the treatment of azoles, metals, and silica solids in wastewater - Google Patents
Combined slurry copper waste and concentrated copper waste for the treatment of azoles, metals, and silica solids in wastewater Download PDFInfo
- Publication number
- WO2024163697A2 WO2024163697A2 PCT/US2024/013926 US2024013926W WO2024163697A2 WO 2024163697 A2 WO2024163697 A2 WO 2024163697A2 US 2024013926 W US2024013926 W US 2024013926W WO 2024163697 A2 WO2024163697 A2 WO 2024163697A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper
- wastewater
- containing solution
- vessel
- oxidizer
- Prior art date
Links
- 239000010949 copper Substances 0.000 title claims abstract description 156
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 151
- 239000002351 wastewater Substances 0.000 title claims abstract description 110
- 239000002699 waste material Substances 0.000 title claims abstract description 23
- 150000003851 azoles Chemical class 0.000 title claims description 36
- 239000002002 slurry Substances 0.000 title description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title description 7
- 229910052751 metal Inorganic materials 0.000 title description 6
- 239000002184 metal Substances 0.000 title description 6
- 150000002739 metals Chemical class 0.000 title description 4
- 239000000377 silicon dioxide Substances 0.000 title description 3
- 239000007787 solid Substances 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract description 58
- 239000007800 oxidant agent Substances 0.000 claims abstract description 46
- 239000004065 semiconductor Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 33
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 23
- 238000005498 polishing Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 67
- -1 hydroxyl radicals Chemical class 0.000 claims description 38
- 238000010977 unit operation Methods 0.000 claims description 20
- 239000012964 benzotriazole Substances 0.000 claims description 19
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 16
- 238000010979 pH adjustment Methods 0.000 claims description 16
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 10
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 8
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 6
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003518 caustics Substances 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000356 contaminant Substances 0.000 description 12
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical class [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 description 8
- 235000012431 wafers Nutrition 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 7
- 239000012028 Fenton's reagent Substances 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical class [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000000153 supplemental effect Effects 0.000 description 3
- HWPNSWJNJROBNW-UHFFFAOYSA-N 2h-benzotriazole;1h-pyrazole Chemical compound C=1C=NNC=1.C1=CC=CC2=NNN=C21 HWPNSWJNJROBNW-UHFFFAOYSA-N 0.000 description 2
- UTMDJGPRCLQPBT-UHFFFAOYSA-N 4-nitro-1h-1,2,3-benzotriazole Chemical class [O-][N+](=O)C1=CC=CC2=NNN=C12 UTMDJGPRCLQPBT-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 241000894007 species Species 0.000 description 2
- UGUHFDPGDQDVGX-UHFFFAOYSA-N 1,2,3-thiadiazole Chemical compound C1=CSN=N1 UGUHFDPGDQDVGX-UHFFFAOYSA-N 0.000 description 1
- YGTAZGSLCXNBQL-UHFFFAOYSA-N 1,2,4-thiadiazole Chemical compound C=1N=CSN=1 YGTAZGSLCXNBQL-UHFFFAOYSA-N 0.000 description 1
- FKASFBLJDCHBNZ-UHFFFAOYSA-N 1,3,4-oxadiazole Chemical compound C1=NN=CO1 FKASFBLJDCHBNZ-UHFFFAOYSA-N 0.000 description 1
- MBIZXFATKUQOOA-UHFFFAOYSA-N 1,3,4-thiadiazole Chemical compound C1=NN=CS1 MBIZXFATKUQOOA-UHFFFAOYSA-N 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical compound C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 description 1
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical class OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 1
- NNRAOBUKHNZQFX-UHFFFAOYSA-N 2H-benzotriazole-4-thiol Chemical class SC1=CC=CC2=C1NN=N2 NNRAOBUKHNZQFX-UHFFFAOYSA-N 0.000 description 1
- YTZPUTADNGREHA-UHFFFAOYSA-N 2h-benzo[e]benzotriazole Chemical compound C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-UHFFFAOYSA-N 0.000 description 1
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 1
- UCFUJBVZSWTHEG-UHFFFAOYSA-N 4-(2-methylphenyl)-2h-triazole Chemical compound CC1=CC=CC=C1C1=CNN=N1 UCFUJBVZSWTHEG-UHFFFAOYSA-N 0.000 description 1
- XQHCBHNLRWLGQS-UHFFFAOYSA-N 4-(3-methylphenyl)-2h-triazole Chemical compound CC1=CC=CC(C2=NNN=C2)=C1 XQHCBHNLRWLGQS-UHFFFAOYSA-N 0.000 description 1
- JQSSWPIJSFUBKX-UHFFFAOYSA-N 5-(2-methylpropyl)-2h-benzotriazole Chemical compound C1=C(CC(C)C)C=CC2=NNN=C21 JQSSWPIJSFUBKX-UHFFFAOYSA-N 0.000 description 1
- PZBQVZFITSVHAW-UHFFFAOYSA-N 5-chloro-2h-benzotriazole Chemical compound C1=C(Cl)C=CC2=NNN=C21 PZBQVZFITSVHAW-UHFFFAOYSA-N 0.000 description 1
- ZWTWLIOPZJFEOO-UHFFFAOYSA-N 5-ethyl-2h-benzotriazole Chemical compound C1=C(CC)C=CC2=NNN=C21 ZWTWLIOPZJFEOO-UHFFFAOYSA-N 0.000 description 1
- SUPSFAUIWDRKKZ-UHFFFAOYSA-N 5-methoxy-2h-benzotriazole Chemical compound C1=C(OC)C=CC2=NNN=C21 SUPSFAUIWDRKKZ-UHFFFAOYSA-N 0.000 description 1
- CCBSHAWEHIDTIU-UHFFFAOYSA-N 5-propyl-2h-benzotriazole Chemical compound CCCC1=CC=C2NN=NC2=C1 CCBSHAWEHIDTIU-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000007980 azole derivatives Chemical class 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning 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
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- JKFAIQOWCVVSKC-UHFFFAOYSA-N furazan Chemical compound C=1C=NON=1 JKFAIQOWCVVSKC-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical group O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000012421 spiking Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- YGNGABUJMXJPIJ-UHFFFAOYSA-N thiatriazole Chemical compound C1=NN=NS1 YGNGABUJMXJPIJ-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/346—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from semiconductor processing, e.g. waste water from polishing of wafers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Definitions
- aspects and embodiments disclosed herein relate to systems and methods for the treatment of wastewater, for example, copper chemical-mechanical polishing (CMP) wastewater including organic contaminants such as azoles.
- CMP copper chemical-mechanical polishing
- the methods disclosed herein provide for the destruction of organic contaminants in the wastewater utilizing a modified Fenton’s reagent utilizing copper from combined waste streams of a semiconductor manufacturing facility as a catalyzing agent.
- a method for removing organic compounds from a copper-containing solution comprises producing the copper- containing solution from a mixture of wastewater from a copper chemical mechanical polishing (CMP) operation of a semiconductor manufacturing facility and a concentrated copper waste stream (CCW) from the semiconductor manufacturing facility; and introducing an oxidizer into the copper-containing solution, the copper catalyzing production of hydroxyl radicals from the oxidizer that react with the organic compounds.
- CMP copper chemical mechanical polishing
- CCW concentrated copper waste stream
- the method further comprises maintaining a pH of the copper- containing solution in the vessel at a level at which the copper catalyzes the production of the hydroxyl radicals from the oxidizer.
- the method further comprises maintaining the pH of the copper- containing solution in the vessel between about 2 and about 4.
- the method further comprises maintaining a temperature of the copper-containing solution in the vessel at between about 55°C and about 65°C.
- introducing the oxidizer into the copper-containing solution includes introducing hydrogen peroxide into the copper-containing solution.
- the method further comprises maintaining a concentration of hydrogen peroxide in the copper-containing solution in the vessel of 250 mg/L or more.
- the method further comprises obtaining the hydrogen peroxide from a waste stream from the semiconductor manufacturing facility.
- producing the copper-containing solution includes mixing at least one part of the CCW with 25 parts of the CMP wastewater or at least one part of the CCW with 10 parts of the CMP wastewater.
- removing the organic compounds from the copper-containing solution includes removing one or more azole compounds from the copper-containing solution.
- producing the copper-containing solution includes mixing the CCW with the CMP wastewater in an amount sufficient to provide 20 parts by weight copper per part by weight of the one or more azole compounds.
- removing the organic compounds from the copper-containing solution includes removing one or more of 1,2,4-Triazole, IH-Benzotriazole pyrazole, Benzotriazole, 5-methyl IH-benzotriazole (Tolutriazole), or 3-amino 1.2.4-triazole from the copper-containing solution.
- a system for removing organic compounds from wastewater from a semiconductor manufacturing facility comprising a vessel fluidly connectable to a source of the wastewater, a source of copper configured to introduce copper into the wastewater in the vessel, the source of copper including a concentrated copper waste stream from the semiconductor manufacturing facility; a source of oxidizer configured to introduce the oxidizer into the wastewater in the vessel, and a source of pH adjustment chemical configured to introduce the pH adjustment chemical into the wastewater in the vessel.
- the system further comprises a pH monitor disposed within the vessel, and a controller configured to control the source of pH adjustment chemical to introduce the pH adjustment chemical into the wastewater in the vessel at a quantity' and rate sufficient to maintain the pH of the wastewater at a level at which the copper catalyzes production of hydroxyl radicals from the oxidizer.
- the controller is configured to control the source of pH adjustment chemical to introduce the pH adjustment chemical into the wastewater in the vessel at a quantity and rate sufficient to maintain the pH of the wastewater at between about 2 and about 4.
- the system further comprises a heater, the controller further configured to control the heater to maintain a temperature of the wastewater in the vessel at between about 55°C and about 65°C.
- the source of oxidizer is a source of hydrogen peroxide
- the controller is further configured to control the source of oxidizer to maintain a concentration of hydrogen peroxide in the wastewater in the vessel at 250 mg/L or more.
- the source of hydrogen peroxide includes a waste stream of the semiconductor manufacturing facility.
- the wastewater includes one or more anti-corrosives for copper and the system is configured to decompose the anti -corrosives for copper with hydroxyl radicals produced from the oxidizer with the copper acting as a catalyst from the production of the hydroxyl radicals.
- the wastewater includes one or more azole compounds and the system is configured to decompose the one or more azoles with hydroxyl radicals produced from the oxidizer with the copper acting as a catalyst from the production of the hydroxyl radicals.
- the wastewater includes one or more of 1,2,4-Triazole, 1H- Benzotriazole pyrazole, Benzotriazole, 5-methyl IH-benzotriazole (Tolutriazole), or 3-amino 1,2,4-triazole and the system is configured to decompose the one or more of 1,2,4-Triazole, 1H- Benzotriazole pyrazole, Benzotriazole, Tolutriazole, or 3-amino 1,2,4-triazole with hydroxyl radicals produced from the oxidizer with the copper acting as a catalyst from the production of the hydroxyl radicals.
- the source of wastewater is a unit operation at the semiconductor manufacturing facility.
- the source of wastewater is a copper CMP operation at the semiconductor manufacturing facility.
- the source of copper includes a copper plating operation at the semiconductor manufacturing facility.
- FIG. 1 illustrates an example of a system as disclosed herein.
- the chemical mechanical polishing (CMP) planarization process involves a polishing slurry' comprising an oxidant, and abrasive, complexing agents, and additional additives to remove and/or etch semiconducting wafers during the manufacturing process.
- the polishing is performed with a polishing pad to remove excess copper from the semiconductor wafers. Silicon, copper, and various trace metals are removed from the silicon structure via the polishing slu '.
- the polishing slurry is introduced to the silicon wafer on a planarization table in conjunction with polishing pads. Oxidizing agents and etching solutions are introduced to control the removal of material.
- Deionized water rinses are generally employed to remove debris from the silicon wafer. UPW from reverse osmosis (RO), demineralized, and polished water may also be used in the semiconductor fabrication facility tools to rinse the silicon wafer.
- RO reverse osmosis
- H2O2 hydrogen peroxide
- An oxidizer of hydrogen peroxide (H2O2) typically is used to help dissolve the copper from the microchip. Accordingly, hydrogen peroxide (H2O2) at a level of about 300 ppm and higher also can be present in the byproduct polishing slurry wastewater.
- azole-type anticorrosives for copper have an excellent anticorrosive effect.
- the azole-type anticorrosives for copper typically have a chemically stable structure and are not easily biodegraded.
- an oxidizing agent having high oxidizing power such as ozone, ultraviolet light, or hydrogen peroxide, or by an advanced oxidation process in which these oxidizing agents are combined, and then treated water is discharged or collected.
- the azole-type anticorrosives for copper are chemically stable, even when using of an oxidizing agent having high oxidizing power, such as ozone, addition of a large amount thereof is required for oxidative decomposition of the azole- type anticorrosives for copper, thus posing a large problem in terms of cost.
- an oxidizing agent having high oxidizing power such as ozone
- addition of a large amount thereof is required for oxidative decomposition of the azole- type anticorrosives for copper, thus posing a large problem in terms of cost.
- the number of fine polishing steps has been increasing, and along with this, the amount of polishing wastewater discharged has been increasing. Therefore, the increase in cost due to an increase in the capacity of wastewater treatment equipment has become a problem.
- Fenton’s reagent is often used for the treatment of organic compounds. Fenton’s reagent may be produced by adding 10 parts of peroxide to 1 part of ferrous iron (ferrous sulfate) for every 0.3 parts of organic compounds.
- Fenton’s reagent is effective when treating some azoles, such as pyrazole.
- lab tests have shown that other forms of azoles such as 1,2,4-Triazole are not decomposed when exposed to Fenton’s reagent.
- azoles are often used in facilities that manufacture computer chips as an anticorrosive additive. These facilities also generally have high strength copper bearing wastewaters from the CMP process that, once spent, are treated and disposed of at a cost to the facility.
- the use of a waste copper stream in place of iron in Fenton’s reagent (a Fenton’s-like reagent) is used to treat and degrade azole compounds in wastewater. Testing has shown that 1,2,4-Triazole.
- Tolytriazole can all be treated using copper-substituted Fenton’s reagent.
- waste hydrogen peroxide which contained the azole to be treated
- waste copper sulfate which can be used in place of iron sulfate in the Fenton’s reaction w as found to produce an oxidantcontaining solution which successfully degraded the azole.
- copper is substituted for iron in a modified Fenton’s reaction, referred to herein as a Fenton’s-like reaction.
- a waste copper stream from a semiconductor production facility may be used as the source of the copper.
- the w aste copper may be present in the effluent of a copper CMP process, referred to as slurry copper w aste (SCW) herein.
- SCW slurry copper w aste
- a combined SCW and concentrated copper waste (CCW) stream may be used as a source of copper for producing a Fenton’s-like reagent (using Cu as a catalyst for the production of hydroxy radicals from H2O2 instead of iron as in a traditional Fenton’s reagent) for the treatment of azoles, metals (e.g., copper, cobalt, and iron), and silica solids in wastewater.
- the two wastewaters are blended at a 1 :25 ratio (CCW: SCW) or greater, for example, a 1: 10 ratio (CCW: SCW) or greater.
- additional copper for example, in the form of a copper sulfate solution, may be added to the combined CCW/SCW to provide additional copper to act as a catalyst in the Fenton’s-like reaction.
- the combined CCW/SCW or the combined CCW/SCW after dosing with additional copper may include 5,000 mg/L of dissolved copper or more, for example, 6,000 mg/L or 7,000 mg/L or more of dissolved copper or a ratio of up to 10: 1, 15: 1, or 20: 1 copper: azoles by weight or more in the wastewater to be treated.
- the wastewater from semiconductor manufacturing facilities or other industrial sources may include high levels of azoles, for example, from about 20 mg/1 up to about 200 mg/1 total azoles or greater, that are used as anticorrosive agents for copper during the wafer planarization and polishing process.
- the wastewater from these processes may also include heavy metals, additional organic compounds, for example, alcohols, and/or surfactants such as ammonium salts, and inorganic abrasives, such as colloidal silica, all of which should be removed prior to discharge of the wastewater.
- additional contaminants may be present at levels from about 0.01 wt% up to about 1 wt%.
- the wastewater may further have a high background total organic carbon (TOC) concentration, with the total azoles comprising a portion of the TOC.
- TOC total organic carbon
- oxidizers such as hydrogen peroxide (H2O2) are generally used to assist in dissolving copper from microchips and may be present in CMP wastewater at concentrations exceeding 1,000 mg/L or 0.1 wt%.
- Azoles are not currently regulated for maximum contaminant levels (MCL) by regulator ⁇ ' authorities in the United States but are believed to have a negative impact on the environment upon discharge into open waterways. Recent evidence has indicated bioaccumulation of azoles in fish and incidences of toxicity of naturally occurring algae blooms, necessitating their removal from process water before discharge.
- MCL maximum contaminant levels
- azole compounds are widely used in the semiconductor industry as anticorrosive agents for copper during silicon wafer processing.
- examples of such azole compounds include, but are not limited to, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, selenazole, 1,2,3-triazole, 1,2,4-triazole, 1,2,5- oxadiazole.
- azole derivatives include compounds having a fused ring of an azole ring and a benzene ring or the like, such as indazole, benzimidazole, benzotriazole, and benzothiazole, and further include derivatives thereof, such as alkylbenzotriazoles (e.g., benzotriazole, o-tolyltriazole, m-tolyl tri azole, -lolvltnazole. 5-ethylbenzotriazole.
- alkylbenzotriazoles e.g., benzotriazole, o-tolyltriazole, m-tolyl tri azole, -lolvltnazole. 5-ethylbenzotriazole.
- a semiconductor manufacturing facility 110 typically includes hundreds of unit operations, three of which are identified in FIG. 1.
- the unit operations identified in FIG. 1 are a copper CMP unit operation 120, a unit operation 130 that produces wastewater with a high concentration of dissolved copper, for example, a copper plating operation, and a unit operation 140 that produces wastewater having a high concentration of hydrogen peroxide, for example, one of the wafer cleaning unit operations within the semiconductor manufacturing facility 110.
- the disclosed system is utilized to decompose organic contaminants such as azoles present in wastewater from the copper CMP unit operation 120 utilizing a Fenton’ s-like reaction in which copper is utilized to catalyze the production of hydroxyl radicals from hydrogen peroxide.
- the hydroxyl radicals decompose the organic contaminants by oxidation into less objectional byproducts such as nitrogen oxides (NO2/NO3), carbon dioxide, and water.
- Wastewater from the CMP unit operation 120 is directed into a vessel 150, for example, by a pump Pl.
- An oxidizer for example, hydrogen peroxide from a source of oxidizer 160 is added to the wastew ater in the vessel 150, for example, using another pump P4 in an amount and at a rate sufficient to maintain a concentration of hydrogen peroxide in the vessel at a desired level, for example, 300 mg/L or greater, to facilitate reactions resulting in decomposition of organic compounds in the wastewater.
- the addition of oxidizer from the source of oxidizer 160 may be supplemented by the addition of hydrogen peroxide-containing wastewater from the unit operation 140, for example, using pump P3. If the hydrogen peroxide- containing wastewater from the unit operation 140 includes sufficient hydrogen peroxide, it may be utilized as the sole source of hydrogen peroxide added to the wastewater in the vessel 150.
- a persulfate salt such as ammonium persulfate, potassium persulfate, and/or sodium persulfate, may be utilized as the oxidizer. Aspects and embodiments disclosed herein are not limited by the type of oxidant added in the treatment system. Peroxides produce hydroxyl and hydroperoxyl radicals and persulfates produce persulfate radicals when reacting with dissolved copper in the vessel 150.
- a source of pH adjustment chemical 170 for example, a source of sulfuric acid and/or sodium hydroxide may add pH adjustment agent into the wastewater in the vessel 150 in an amount and at a rate sufficient to maintain the pH of the wastewater in the vessel at a desired level, for example, between 2 and 4 or about 3 to facilitate reactions resulting in decomposition of organic compounds in the wastew ater.
- a heater or heat exchanger 210 may also be present in the vessel and may be used to maintain the temperature of the wastewater in the vessel at a temperature suitable to facilitate decomposition of organic compounds such as azoles in the wastewater via a Fenton’s-like reaction within a desired timeframe. This temperature may be, for example, between 55°C and 65°C or about 60°C.
- the w astew ater from the CMP unit operation 120 may include sufficient copper, for example, in the form of copper sulfate, to catalyze production of hydroxyl radicals from the hydrogen peroxide in the vessel 150 in a Fenton’s-like reaction which will decompose one or more organic species in the wastewater in the vessel 150.
- Byproducts of the decomposition of the organic contaminants such as nitrogen oxides (NO2/NO3) and carbon dioxide may exit the vessel 150 through a vent V.
- the one or more organic species may include one or more azoles, for example, one or more of 1,2,4-Triazole, IH-Benzotriazole, or Methylbenzotriazole: 4,5 Tolytriazole which may have been present in the wastewater from the CMP unit operation 120.
- the Fenton’s-like reagent used for the decomposition of the azoles may be formed by adding about 500 mg/1 to about 3.000 mg/1 of an oxidant, such as hydrogen peroxide or a persulfate salt, to about 50 mg/1 to about 300 mg/1 of a soluble copper compound (e g., copper (Cu 2+ ) sulfate).
- the persulfate salt and the hydroxyl, hydroperoxyl, and persulfate radicals formed by the oxidation of Cu 2+ or the reduction of Cu 3+ may react with and decompose the azoles in the CMP wastewater into primarily nitrogen oxides (NO2/NO3), carbon dioxide, and water.
- NO2/NO3 nitrogen oxides
- carbon dioxide carbon dioxide
- water water
- One or more sensors or monitors may be present in the vessel 150 in contact with the wastewater in the vessel.
- the one or more sensors S may be in communication with a controller 190.
- the controller 190 may be a conventional computer including a conventional processor, for example, a Core® processor from the Intel Corporation and running a conventional operating system such as one of the versions of Windows® from the Microsoft Corporation and programmed to perform the functions disclosed herein.
- the controller may optionally be or include a specially programmed controller such as an Application Specific Integrated Circuit (ASIC) programmed to perform the functions disclosed herein.
- ASIC Application Specific Integrated Circuit
- the controller 190 is programmed or otherwise configured to control the source of pH adjustment chemical 170 to introduce the pH adjustment chemical into the wastewater in the vessel 150 at a quantity and rate sufficient to maintain the pH of the wastewater at a level at which the copper catalyzes production of hydroxyl radicals from the oxidizer.
- the controller 190 may also control operation of the heat exchanger or heater 210 and any of the pumps P1-P7 to control, e.g., introduction of wastewater from the CMP unit operation 120, oxidizer from the source of oxidizer 160, CCW from the unit operation 130, hydrogen peroxide-containing wastewater from the unit operationl40, supplemental copper solution from the source 200, and removal of treated wastewater from the vessel 150.
- the wastewater from the CMP unit operation 120 may not contain sufficient copper to catalyze production of sufficient hydroxyl radicals for decomposition of organic contaminants in the wastewater from the CMP unit operation 120 to levels that are as low as might be desired.
- additional copper may be added to the wastewater in the vessel 150 from, for example, the unit operation 130 that produces the wastewater with the high concentration of dissolved copper (the CCW) through a pump P2 operated by the controller 190.
- the two wastewaters may be blended or introduced into the vessel 150 at a 1 :25 ratio (CCW:SCW) or greater, for example, a 1: 10 ratio (CCW: SCW) or greater.
- additional copper for example, in the form of a copper sulfate solution, may be added to the combined CCW/SCW from a source 200 of supplemental copper solution through, for example, another pump P7 to provide additional copper to act as a catalyst in the Fenton’s-like reaction.
- the combined CCW/SCW or the combined CCW/SCW after dosing with additional copper may include 5,000 mg/L of dissolved copper or more, for example, 6,000 mg/L or 7,000 mg/L or more of dissolved copper or a ratio of up to 10: 1, 15: 1, or 20: 1 copper: azoles by weight or more in the wastewater to be treated.
- Wastewater from which organic compounds have been removed by decomposition by a Fentons ’s-like reaction as disclosed herein in the vessel 150 may exit the vessel and be directed, for example, by a pump P6 into a post-treatment system 180.
- the post-treatment system 180 may be used to remove residual copper and other undesired components from the partially treated wastewater exiting the vessel 150 using methods known in the art and may produce treated water that may be discharged to the environment, recycled, or sent for further treatment or disposal.
- aspects and embodiments disclosed herein are also directed to a method for removing organic compounds, for example, one or more azoles from a copper-containing solution, for example, wastewater from a chemical mechanical polishing unit operation of a semiconductor manufacturing facility utilizing a Fenton’s-like reagent.
- the copper-containing solution may be produced from a mixture of wastewater from a copper chemical mechanical polishing (CMP) operation of the semiconductor manufacturing facility and a concentrated copper waste stream (CCW) from the semiconductor manufacturing facility.
- CMP copper chemical mechanical polishing
- CCW concentrated copper waste stream
- the method may include introducing an oxidizer into the copper-containing solution, the copper catalyzing production of hydroxyl radicals from the oxidizer that react with the organic compounds.
- the pH of the copper- containing solution in the vessel may be maintained at a level at which the copper catalyzes the production of the hydroxyl radicals from the oxidizer, for example between 2 and 4.
- the temperature of the copper-containing solution in the vessel may be maintained at between about 55°C and about 65°C.
- Introducing the oxidizer into the copper-containing solution may include introducing hydrogen peroxide into the copper-containing solution.
- the concentration of hydrogen peroxide in the copper-containing solution in the vessel may be maintained at 250 mg/L or more.
- the hydrogen peroxide may be obtained from a waste stream from the semiconductor manufacturing facility.
- Producing the copper-containing solution may includes mixing at least one part of the CCW with 25 parts of the CMP wastewater or at least one part of the CCW with 10 parts of the CMP wastewater.
- Producing the copper-containing solution may include combining the CCW with the CMP wastewater in an amount sufficient to provide 10 parts by weight copper per part by weight of the one or more azole compounds.
- Removing the organic compounds from the copper-containing solution may include removing one or more of 1,2,4-Triazole, IH-Benzotriazole, or Methylbenzotriazole: 4,5 Tolytriazole from the copper- containing solution.
- the 10: 1 blend removed more TOC than the 25: 1 blend but still only removed 32% TOC.
- the term ‘‘plurality” refers to two or more items or components.
- the terms “comprising,” “including,” “carry ing,” “having,” “containing,” and “involving.” whether in the written description or the claims and the like, are open-ended terms, i.e.. to mean “including but not limited to.” Thus, the use of such terms is meant to encompass the items listed thereafter, and equivalents thereof, as well as additional items. Only the transitional phrases “consisting of’ and “consisting essentially of,” are closed or semi-closed transitional phrases, respectively, with respect to the claims.
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Abstract
A method for removing organic compounds from a copper-containing solution includes producing the copper-containing solution from a mixture of wastewater from a copper chemical mechanical polishing (CMP) operation of a semiconductor manufacturing facility and a concentrated copper waste stream (CCW) from the semiconductor manufacturing facility, and introducing an oxidizer into the copper-containing solution, the copper catalyzing production of hydroxyl radicals from the oxidizer that react with the organic compounds.
Description
COMBINED SLURRY COPPER WASTE AND CONCENTRATED COPPER WASTE
FOR THE TREATMENT OF AZOLES. METALS, AND SILICA SOLIDS IN WASTEWATER
FIELD OF TECHNOLOGY
Aspects and embodiments disclosed herein relate to systems and methods for the treatment of wastewater, for example, copper chemical-mechanical polishing (CMP) wastewater including organic contaminants such as azoles. The methods disclosed herein provide for the destruction of organic contaminants in the wastewater utilizing a modified Fenton’s reagent utilizing copper from combined waste streams of a semiconductor manufacturing facility as a catalyzing agent.
SUMMARY
In accordance with one aspect, there is provided a method for removing organic compounds from a copper-containing solution. The method comprises producing the copper- containing solution from a mixture of wastewater from a copper chemical mechanical polishing (CMP) operation of a semiconductor manufacturing facility and a concentrated copper waste stream (CCW) from the semiconductor manufacturing facility; and introducing an oxidizer into the copper-containing solution, the copper catalyzing production of hydroxyl radicals from the oxidizer that react with the organic compounds.
In some embodiments, the method further comprises maintaining a pH of the copper- containing solution in the vessel at a level at which the copper catalyzes the production of the hydroxyl radicals from the oxidizer.
In some embodiments, the method further comprises maintaining the pH of the copper- containing solution in the vessel between about 2 and about 4.
In some embodiments, the method further comprises maintaining a temperature of the copper-containing solution in the vessel at between about 55°C and about 65°C.
In some embodiments, introducing the oxidizer into the copper-containing solution includes introducing hydrogen peroxide into the copper-containing solution.
In some embodiments, the method further comprises maintaining a concentration of hydrogen peroxide in the copper-containing solution in the vessel of 250 mg/L or more.
In some embodiments, the method further comprises obtaining the hydrogen peroxide from a waste stream from the semiconductor manufacturing facility.
In some embodiments, producing the copper-containing solution includes mixing at least one part of the CCW with 25 parts of the CMP wastewater or at least one part of the CCW with 10 parts of the CMP wastewater.
In some embodiments, removing the organic compounds from the copper-containing solution includes removing one or more azole compounds from the copper-containing solution.
In some embodiments, producing the copper-containing solution includes mixing the CCW with the CMP wastewater in an amount sufficient to provide 20 parts by weight copper per part by weight of the one or more azole compounds.
In some embodiments, removing the organic compounds from the copper-containing solution includes removing one or more of 1,2,4-Triazole, IH-Benzotriazole pyrazole, Benzotriazole, 5-methyl IH-benzotriazole (Tolutriazole), or 3-amino 1.2.4-triazole from the copper-containing solution.
In accordance with another aspect, there is provided a system for removing organic compounds from wastewater from a semiconductor manufacturing facility. The system comprises a vessel fluidly connectable to a source of the wastewater, a source of copper configured to introduce copper into the wastewater in the vessel, the source of copper including a concentrated copper waste stream from the semiconductor manufacturing facility; a source of oxidizer configured to introduce the oxidizer into the wastewater in the vessel, and a source of pH adjustment chemical configured to introduce the pH adjustment chemical into the wastewater in the vessel.
In some embodiments, the system further comprises a pH monitor disposed within the vessel, and a controller configured to control the source of pH adjustment chemical to introduce the pH adjustment chemical into the wastewater in the vessel at a quantity' and rate sufficient to maintain the pH of the wastewater at a level at which the copper catalyzes production of hydroxyl radicals from the oxidizer.
In some embodiments, the controller is configured to control the source of pH adjustment chemical to introduce the pH adjustment chemical into the wastewater in the vessel at a quantity and rate sufficient to maintain the pH of the wastewater at between about 2 and about 4.
In some embodiments, the system further comprises a heater, the controller further configured to control the heater to maintain a temperature of the wastewater in the vessel at between about 55°C and about 65°C.
In some embodiments, the source of oxidizer is a source of hydrogen peroxide, and the controller is further configured to control the source of oxidizer to maintain a concentration of hydrogen peroxide in the wastewater in the vessel at 250 mg/L or more.
In some embodiments, the source of hydrogen peroxide includes a waste stream of the semiconductor manufacturing facility.
In some embodiments, the wastewater includes one or more anti-corrosives for copper and the system is configured to decompose the anti -corrosives for copper with hydroxyl radicals produced from the oxidizer with the copper acting as a catalyst from the production of the hydroxyl radicals.
In some embodiments, the wastewater includes one or more azole compounds and the system is configured to decompose the one or more azoles with hydroxyl radicals produced from the oxidizer with the copper acting as a catalyst from the production of the hydroxyl radicals.
In some embodiments, the wastewater includes one or more of 1,2,4-Triazole, 1H- Benzotriazole pyrazole, Benzotriazole, 5-methyl IH-benzotriazole (Tolutriazole), or 3-amino 1,2,4-triazole and the system is configured to decompose the one or more of 1,2,4-Triazole, 1H- Benzotriazole pyrazole, Benzotriazole, Tolutriazole, or 3-amino 1,2,4-triazole with hydroxyl radicals produced from the oxidizer with the copper acting as a catalyst from the production of the hydroxyl radicals.
In some embodiments, the source of wastewater is a unit operation at the semiconductor manufacturing facility.
In some embodiments, the source of wastewater is a copper CMP operation at the semiconductor manufacturing facility.
In some embodiments, the source of copper includes a copper plating operation at the semiconductor manufacturing facility.
BRIEF DESCRIPTION OF THE DRAWING
The accompanying drawing is not intended to be drawn to scale. In the drawing, each identical or nearly identical component that is illustrated is represented by a like numeral. For purposes of clarity, not every component may be labeled. In the drawings:
FIG. 1 illustrates an example of a system as disclosed herein.
DETAILED DESCRIPTION
The chemical mechanical polishing (CMP) planarization process involves a polishing slurry' comprising an oxidant, and abrasive, complexing agents, and additional additives to remove and/or etch semiconducting wafers during the manufacturing process. The polishing is performed with a polishing pad to remove excess copper from the semiconductor wafers. Silicon, copper, and various trace metals are removed from the silicon structure via the
polishing slu '. The polishing slurry is introduced to the silicon wafer on a planarization table in conjunction with polishing pads. Oxidizing agents and etching solutions are introduced to control the removal of material. Deionized water rinses are generally employed to remove debris from the silicon wafer. UPW from reverse osmosis (RO), demineralized, and polished water may also be used in the semiconductor fabrication facility tools to rinse the silicon wafer.
An oxidizer of hydrogen peroxide (H2O2) typically is used to help dissolve the copper from the microchip. Accordingly, hydrogen peroxide (H2O2) at a level of about 300 ppm and higher also can be present in the byproduct polishing slurry wastewater.
In fabrication processes of semiconductor devices, large amounts of wastewater containing anticorrosives for copper are discharged from CMP steps for performing surface polishing of copper when copper wiring is installed. Therefore, treatment of the wastewater is desirable to prevent discharge of undesirable contaminants to the environment.
Among anticorrosives for copper, in particular, azole-type anticorrosives for copper have an excellent anticorrosive effect. However, the azole-type anticorrosives for copper typically have a chemically stable structure and are not easily biodegraded. Thus, conventionally, in treating wastewater containing an azole-type anticorrosive for copper discharged from the process, the azole-type anticorrosive for copper is decomposed using an oxidizing agent having high oxidizing power, such as ozone, ultraviolet light, or hydrogen peroxide, or by an advanced oxidation process in which these oxidizing agents are combined, and then treated water is discharged or collected.
However, as described above, since the azole-type anticorrosives for copper are chemically stable, even when using of an oxidizing agent having high oxidizing power, such as ozone, addition of a large amount thereof is required for oxidative decomposition of the azole- type anticorrosives for copper, thus posing a large problem in terms of cost. In particular, in recent years, with the increase in the degree of integration in semiconductor devices, the number of fine polishing steps has been increasing, and along with this, the amount of polishing wastewater discharged has been increasing. Therefore, the increase in cost due to an increase in the capacity of wastewater treatment equipment has become a problem.
Fenton’s reagent is often used for the treatment of organic compounds. Fenton’s reagent may be produced by adding 10 parts of peroxide to 1 part of ferrous iron (ferrous sulfate) for every 0.3 parts of organic compounds.
Fenton’s reagent is effective when treating some azoles, such as pyrazole. However, lab tests have shown that other forms of azoles such as 1,2,4-Triazole are not decomposed when exposed to Fenton’s reagent.
As discussed above, azoles are often used in facilities that manufacture computer chips as an anticorrosive additive. These facilities also generally have high strength copper bearing wastewaters from the CMP process that, once spent, are treated and disposed of at a cost to the facility. In one embodiment, the use of a waste copper stream in place of iron in Fenton’s reagent (a Fenton’s-like reagent) is used to treat and degrade azole compounds in wastewater. Testing has shown that 1,2,4-Triazole. IH-Benzotriazole, and Methylbenzotriazole: 4,5 Tolytriazole can all be treated using copper-substituted Fenton’s reagent. In one test waste hydrogen peroxide (which contained the azole to be treated), and waste copper sulfate, which can be used in place of iron sulfate in the Fenton’s reaction w as found to produce an oxidantcontaining solution which successfully degraded the azole.
In some embodiments, copper is substituted for iron in a modified Fenton’s reaction, referred to herein as a Fenton’s-like reaction. A waste copper stream from a semiconductor production facility may be used as the source of the copper. The w aste copper may be present in the effluent of a copper CMP process, referred to as slurry copper w aste (SCW) herein. More specifically, in some aspects and embodiments, a combined SCW and concentrated copper waste (CCW) stream may be used as a source of copper for producing a Fenton’s-like reagent (using Cu as a catalyst for the production of hydroxy radicals from H2O2 instead of iron as in a traditional Fenton’s reagent) for the treatment of azoles, metals (e.g., copper, cobalt, and iron), and silica solids in wastewater. In some embodiments, the two wastewaters are blended at a 1 :25 ratio (CCW: SCW) or greater, for example, a 1: 10 ratio (CCW: SCW) or greater. In some embodiments, additional copper, for example, in the form of a copper sulfate solution, may be added to the combined CCW/SCW to provide additional copper to act as a catalyst in the Fenton’s-like reaction. In some embodiments, the combined CCW/SCW or the combined CCW/SCW after dosing with additional copper may include 5,000 mg/L of dissolved copper or more, for example, 6,000 mg/L or 7,000 mg/L or more of dissolved copper or a ratio of up to 10: 1, 15: 1, or 20: 1 copper: azoles by weight or more in the wastewater to be treated.
As noted above, the wastewater from semiconductor manufacturing facilities or other industrial sources may include high levels of azoles, for example, from about 20 mg/1 up to about 200 mg/1 total azoles or greater, that are used as anticorrosive agents for copper during the wafer planarization and polishing process. The wastewater from these processes may also include heavy metals, additional organic compounds, for example, alcohols, and/or surfactants such as ammonium salts, and inorganic abrasives, such as colloidal silica, all of which should be removed prior to discharge of the wastewater. These additional contaminants may be present at levels from about 0.01 wt% up to about 1 wt%. The wastewater may further have a high
background total organic carbon (TOC) concentration, with the total azoles comprising a portion of the TOC. For example, oxidizers such as hydrogen peroxide (H2O2) are generally used to assist in dissolving copper from microchips and may be present in CMP wastewater at concentrations exceeding 1,000 mg/L or 0.1 wt%.
Azoles are not currently regulated for maximum contaminant levels (MCL) by regulator}' authorities in the United States but are believed to have a negative impact on the environment upon discharge into open waterways. Recent evidence has indicated bioaccumulation of azoles in fish and incidences of toxicity of naturally occurring algae blooms, necessitating their removal from process water before discharge.
As described in US Patent No. 8,801,937, the disclosure of which is herein incorporated by reference in its entirety for all purposes, azole compounds are widely used in the semiconductor industry as anticorrosive agents for copper during silicon wafer processing. Examples of such azole compounds include, but are not limited to, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, selenazole, 1,2,3-triazole, 1,2,4-triazole, 1,2,5- oxadiazole. 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, tetrazole, 1,2,3.4-thiatriazole, any derivatives thereof, amine salts thereof, and metal salts thereof. Examples of azole derivatives include compounds having a fused ring of an azole ring and a benzene ring or the like, such as indazole, benzimidazole, benzotriazole, and benzothiazole, and further include derivatives thereof, such as alkylbenzotriazoles (e.g., benzotriazole, o-tolyltriazole, m-tolyl tri azole, -lolvltnazole. 5-ethylbenzotriazole. 5-n- propylbenzotriazole, 5 -isobutylbenzotri azole, and 4-methylbenzotriazole), alkoxybenzotriazoles (e.g., 5 -methoxy benzotriazole), alkylaminobenzotriazoles, alkylaminosulfonylbenzotriazoles, mercaptobenzotriazoles, hydroxybenzotriazoles, nitrobenzotriazoles (e.g., 4-nitrobenzotriazole), halobenzotriazoles (e.g., 5-chlorobenzotriazole), hydroxy alkylbenzotriazoles, hydrobenzotriazoles, aminobenzotnazoles, (substituted aminomethyl)-tolyltriazole, carboxybenzotriazole, N-alkylbenzotriazoles, bisbenzotriazole, naphthotriazole, mercaptobenzothiazoles, aminobenzothiazole, amine salts thereof, and metal salts thereof.
One embodiment of a system for treating azole-containing wastewater from a semiconductor manufacturing facility is shown schematically in FIG. 1. A semiconductor manufacturing facility 110 typically includes hundreds of unit operations, three of which are identified in FIG. 1. The unit operations identified in FIG. 1 are a copper CMP unit operation 120, a unit operation 130 that produces wastewater with a high concentration of dissolved copper, for example, a copper plating operation, and a unit operation 140 that produces wastewater having a high concentration of hydrogen peroxide, for example, one of the wafer
cleaning unit operations within the semiconductor manufacturing facility 110. The disclosed system is utilized to decompose organic contaminants such as azoles present in wastewater from the copper CMP unit operation 120 utilizing a Fenton’ s-like reaction in which copper is utilized to catalyze the production of hydroxyl radicals from hydrogen peroxide. The hydroxyl radicals decompose the organic contaminants by oxidation into less objectional byproducts such as nitrogen oxides (NO2/NO3), carbon dioxide, and water.
Wastewater from the CMP unit operation 120 is directed into a vessel 150, for example, by a pump Pl. An oxidizer, for example, hydrogen peroxide from a source of oxidizer 160 is added to the wastew ater in the vessel 150, for example, using another pump P4 in an amount and at a rate sufficient to maintain a concentration of hydrogen peroxide in the vessel at a desired level, for example, 300 mg/L or greater, to facilitate reactions resulting in decomposition of organic compounds in the wastewater. In some embodiments, the addition of oxidizer from the source of oxidizer 160 may be supplemented by the addition of hydrogen peroxide-containing wastewater from the unit operation 140, for example, using pump P3. If the hydrogen peroxide- containing wastewater from the unit operation 140 includes sufficient hydrogen peroxide, it may be utilized as the sole source of hydrogen peroxide added to the wastewater in the vessel 150.
In other embodiments, a persulfate salt such as ammonium persulfate, potassium persulfate, and/or sodium persulfate, may be utilized as the oxidizer. Aspects and embodiments disclosed herein are not limited by the type of oxidant added in the treatment system. Peroxides produce hydroxyl and hydroperoxyl radicals and persulfates produce persulfate radicals when reacting with dissolved copper in the vessel 150.
A source of pH adjustment chemical 170, for example, a source of sulfuric acid and/or sodium hydroxide may add pH adjustment agent into the wastewater in the vessel 150 in an amount and at a rate sufficient to maintain the pH of the wastewater in the vessel at a desired level, for example, between 2 and 4 or about 3 to facilitate reactions resulting in decomposition of organic compounds in the wastew ater.
A heater or heat exchanger 210 may also be present in the vessel and may be used to maintain the temperature of the wastewater in the vessel at a temperature suitable to facilitate decomposition of organic compounds such as azoles in the wastewater via a Fenton’s-like reaction within a desired timeframe. This temperature may be, for example, between 55°C and 65°C or about 60°C.
The w astew ater from the CMP unit operation 120 may include sufficient copper, for example, in the form of copper sulfate, to catalyze production of hydroxyl radicals from the hydrogen peroxide in the vessel 150 in a Fenton’s-like reaction which will decompose one or
more organic species in the wastewater in the vessel 150. Byproducts of the decomposition of the organic contaminants such as nitrogen oxides (NO2/NO3) and carbon dioxide may exit the vessel 150 through a vent V. The one or more organic species may include one or more azoles, for example, one or more of 1,2,4-Triazole, IH-Benzotriazole, or Methylbenzotriazole: 4,5 Tolytriazole which may have been present in the wastewater from the CMP unit operation 120. The Fenton’s-like reagent used for the decomposition of the azoles may be formed by adding about 500 mg/1 to about 3.000 mg/1 of an oxidant, such as hydrogen peroxide or a persulfate salt, to about 50 mg/1 to about 300 mg/1 of a soluble copper compound (e g., copper (Cu2+) sulfate).
The Fenton’s-like reaction may occur in accordance with chemical equations (l)-(3):
Cu2+ + H2O2 Cu3+ + HO* + OH ( 1 )
Cu3+ + H2O2 Cu2+ + HOO* + H+ (2)
Cu2+ + S20s2 Cu3+ + SO4*" + SO42 (3)
The persulfate salt and the hydroxyl, hydroperoxyl, and persulfate radicals formed by the oxidation of Cu2+ or the reduction of Cu3+ may react with and decompose the azoles in the CMP wastewater into primarily nitrogen oxides (NO2/NO3), carbon dioxide, and water. Without wishing to be bound by any particular theory, the decomposition of a nitrogenous organic molecule, such as an azole, may occur by the reaction illustrated in equation 4:
CxNyHz + OH* CO2 + NO3 + H2O (4)
One or more sensors or monitors, for example, temperature, pH, ORP, chemical concentration sensors, etc., collectively indicated at “S” may be present in the vessel 150 in contact with the wastewater in the vessel. The one or more sensors S may be in communication with a controller 190. The controller 190 may be a conventional computer including a conventional processor, for example, a Core® processor from the Intel Corporation and running a conventional operating system such as one of the versions of Windows® from the Microsoft Corporation and programmed to perform the functions disclosed herein. The controller may optionally be or include a specially programmed controller such as an Application Specific Integrated Circuit (ASIC) programmed to perform the functions disclosed herein. The controller 190 is programmed or otherwise configured to control the source of pH adjustment chemical 170 to introduce the pH adjustment chemical into the wastewater in the vessel 150 at a quantity
and rate sufficient to maintain the pH of the wastewater at a level at which the copper catalyzes production of hydroxyl radicals from the oxidizer. The controller 190 may also control operation of the heat exchanger or heater 210 and any of the pumps P1-P7 to control, e.g., introduction of wastewater from the CMP unit operation 120, oxidizer from the source of oxidizer 160, CCW from the unit operation 130, hydrogen peroxide-containing wastewater from the unit operationl40, supplemental copper solution from the source 200, and removal of treated wastewater from the vessel 150.
In some embodiments, the wastewater from the CMP unit operation 120 (the SCW) may not contain sufficient copper to catalyze production of sufficient hydroxyl radicals for decomposition of organic contaminants in the wastewater from the CMP unit operation 120 to levels that are as low as might be desired. Accordingly, additional copper may be added to the wastewater in the vessel 150 from, for example, the unit operation 130 that produces the wastewater with the high concentration of dissolved copper (the CCW) through a pump P2 operated by the controller 190. As noted above, in some embodiments, the two wastewaters may be blended or introduced into the vessel 150 at a 1 :25 ratio (CCW:SCW) or greater, for example, a 1: 10 ratio (CCW: SCW) or greater. In some embodiments, additional copper, for example, in the form of a copper sulfate solution, may be added to the combined CCW/SCW from a source 200 of supplemental copper solution through, for example, another pump P7 to provide additional copper to act as a catalyst in the Fenton’s-like reaction. In some embodiments, the combined CCW/SCW or the combined CCW/SCW after dosing with additional copper may include 5,000 mg/L of dissolved copper or more, for example, 6,000 mg/L or 7,000 mg/L or more of dissolved copper or a ratio of up to 10: 1, 15: 1, or 20: 1 copper: azoles by weight or more in the wastewater to be treated.
Wastewater from which organic compounds have been removed by decomposition by a Fentons ’s-like reaction as disclosed herein in the vessel 150 may exit the vessel and be directed, for example, by a pump P6 into a post-treatment system 180. The post-treatment system 180 may be used to remove residual copper and other undesired components from the partially treated wastewater exiting the vessel 150 using methods known in the art and may produce treated water that may be discharged to the environment, recycled, or sent for further treatment or disposal.
Aspects and embodiments disclosed herein are also directed to a method for removing organic compounds, for example, one or more azoles from a copper-containing solution, for example, wastewater from a chemical mechanical polishing unit operation of a semiconductor manufacturing facility utilizing a Fenton’s-like reagent. The copper-containing solution may be
produced from a mixture of wastewater from a copper chemical mechanical polishing (CMP) operation of the semiconductor manufacturing facility and a concentrated copper waste stream (CCW) from the semiconductor manufacturing facility. The method may include introducing an oxidizer into the copper-containing solution, the copper catalyzing production of hydroxyl radicals from the oxidizer that react with the organic compounds. The pH of the copper- containing solution in the vessel may be maintained at a level at which the copper catalyzes the production of the hydroxyl radicals from the oxidizer, for example between 2 and 4. The temperature of the copper-containing solution in the vessel may be maintained at between about 55°C and about 65°C. Introducing the oxidizer into the copper-containing solution may include introducing hydrogen peroxide into the copper-containing solution. The concentration of hydrogen peroxide in the copper-containing solution in the vessel may be maintained at 250 mg/L or more. The hydrogen peroxide may be obtained from a waste stream from the semiconductor manufacturing facility. Producing the copper-containing solution may includes mixing at least one part of the CCW with 25 parts of the CMP wastewater or at least one part of the CCW with 10 parts of the CMP wastewater. Producing the copper-containing solution may include combining the CCW with the CMP wastewater in an amount sufficient to provide 10 parts by weight copper per part by weight of the one or more azole compounds. Removing the organic compounds from the copper-containing solution may include removing one or more of 1,2,4-Triazole, IH-Benzotriazole, or Methylbenzotriazole: 4,5 Tolytriazole from the copper- containing solution.
Example 1
CMP slurry7 wastewater (Slurry' Copper Waste - SCW) and wastewater having a high concentration of Cu (Concentrated Copper Waste - CCW), as well as a 25: 1 mixture of the SCW and CCW from a semiconductor production facility was analyzed and found to include the contaminants listed in Table 1 below:
Testing was performed to determine if the copper was present in the 25: 1 mixture of the SCW and CCW in amount sufficient to catalyze production of sufficient hydroxyl radical to decompose the 1,2,4-Triazole present in the mixture. Details of the test conditions and results are presented in Table 2 below:
1 Sodium Bisulfate - decomposes H2O2
The pH of the blended sample (962 mL SCW + 38 mL CCW) was 3.0. A cumulative dose of 1,680 mg/L H2O2 over the 120-minute reaction time yielded 90% TOC removal and 0.38 mg/1 azole residual (99% removal). These results were achieved without adding iron and show that copper already present in wastewater streams from a semiconduction production facility may be utilized as catalyst for a Fenton’ s-like reaction to successfully remove organic contaminants, including azoles, from those same wastewater streams. Example 2
Further testing was performed to evaluate whether a Fenton’s like reaction as disclosed herein could successfully decompose organic compounds such as azoles from wastewater from a semiconductor manufacturing facility under a simulated worst case scenario for concentration of contaminants in the wastewater. 25:1 SCW: CCW and 10: 1 SCW: CCW wastewater mixtures were spiked with additional 1,2,4-Triazole to result in wastewater mixtures with the copper and azole concentrations shown in Table 3 below.
Table 3 - Simulated worst case wastewater mixtures
The test conditions and results for TOC removal from the simulated worst case wastewaters are shown in Table 4 below.
The 10: 1 blend removed more TOC than the 25: 1 blend but still only removed 32% TOC.
One more Fenton’ s-like reaction test was conducted to determine the ratio of copper to azole required to get around 70% TOC removal, which should correspond to more than 90% azole removal. The copper to azole ratio versus TOC removal was extrapolated from the results above, and it was determined that the concentration of copper required would be -7,000 mg/L. a ratio of about 20 copper/azoles by weight.
This Fenton’s-like reaction test was performed by spiking the 25: 1 blend, which contained around 690 mg/L Cu with 6,330 mg/L Cu (9,582 mg/L CuSO4). The results are shown in Table 5 along with the same blend sample with no copper spiked for comparison.
Table 5 - TOC removal from simulated worst case wastewaters with supplemental Cu
The TOC removal was greatly improved with the addition of copper at the beginning of the test suggesting that a ratio of 20 copper/azoles or higher may provide for successful decomposition of organic compounds in a combined SCW:CCW wastewater by a Fenton’s- like reaction.
The phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. As used herein, the term ‘‘plurality” refers to two or more items or components. The terms “comprising,” “including,” “carry ing,” “having,” “containing,” and “involving.” whether in the written description or the claims and the like, are open-ended terms, i.e.. to mean “including but not limited to.” Thus, the use of such terms is meant to encompass the items listed thereafter, and equivalents thereof, as well as additional items. Only the transitional phrases “consisting of’ and “consisting essentially of,” are closed or semi-closed transitional phrases, respectively, with respect to the claims. Use of ordinal terms such as “first,” “second,” “third.” and the like in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are performed, but are used merely as labels to distinguish one claim
element having a certain name from another element having a same name (but for use of the ordinal term) to distinguish the claim elements.
Claims
1. A method for removing organic compounds from a copper-containing solution, the method comprising: producing the copper-containing solution from a mixture of wastewater from a copper chemical mechanical polishing (CMP) operation of a semiconductor manufacturing facility and a concentrated copper waste stream (CCW) from the semiconductor manufacturing facility; and introducing an oxidizer into the copper-containing solution, the copper catalyzing production of hydroxyl radicals from the oxidizer that react with the organic compounds.
2. The method of claim 1, further comprising maintaining a pH of the copper-containing solution in the vessel at a level at which the copper catalyzes the production of the hydroxyl radicals from the oxidizer.
3. The method of claim 2, further comprising maintaining the pH of the copper- containing solution in the vessel between about 2 and about 4.
4. The method of claim 1, further comprising maintaining a temperature of the copper- containing solution in the vessel at between about 55°C and about 65°C.
5. The method of claim 1, wherein introducing the oxidizer into the copper-containing solution includes introducing hydrogen peroxide into the copper-containing solution.
6. The method of claim 5, further comprising maintaining a concentration of hydrogen peroxide in the copper-containing solution in the vessel of 250 mg/L or more.
7. The method of claim 5, further comprising obtaining the hydrogen peroxide from a waste stream from the semiconductor manufacturing facility.
8. The method of claim 1, wherein producing the copper-containing solution includes mixing at least one part of the CCW with 25 parts of the CMP wastewater.
9. The method of claim 1, wherein removing the organic compounds from the copper- containing solution includes removing one or more azole compounds from the copper- containing solution.
10. The method of claim 9, wherein producing the copper-containing solution includes mixing the CCW with the CMP wastewater in an amount sufficient to provide 20 parts byweight copper per part by weight of the one or more azole compounds.
11. The method of claim 9, wherein removing the organic compounds from the copper- containing solution includes removing one or more of 1,2,4-Triazole, IH-Benzotriazole pyrazole. Benzotriazole, 5-methyl IH-benzotriazole (Tolutriazole), or 3-amino 1.2.4-triazole from the copper-containing solution.
12. A system for removing organic compounds from wastewater from a semiconductor manufacturing facility, the system comprising: a vessel fluidly connectable to a source of the wastewater; a source of copper configured to introduce copper into the wastewater in the vessel, the source of copper including a concentrated copper waste stream from the semiconductor manufacturing facility; a source of oxidizer configured to introduce the oxidizer into the wastewater in the vessel; and a source of pH adjustment chemical configured to introduce the pH adjustment chemical into the wastewater in the vessel.
13. The system of claim 12, further comprising: a pH monitor disposed within the vessel; and a controller configured to control the source of pH adjustment chemical to introduce the pH adjustment chemical into the wastewater in the vessel at a quantity- and rate sufficient to maintain the pH of the wastewater at a level at which the copper catalyzes production of hydroxyl radicals from the oxidizer.
14. The system of claim 13, wherein the controller is configured to control the source of pH adjustment chemical to introduce the pH adjustment chemical into the wastewater in the
vessel at a quantity and rate sufficient to maintain the pH of the wastewater at between about 2 and about 4.
15. The system of claim 13, further comprising a heater, the controller further configured to control the heater to maintain a temperature of the wastewater in the vessel at between about 55°C and about 65°C.
16. The system of claim 13, wherein the source of oxidizer is a source of hydrogen peroxide, and the controller is further configured to control the source of oxidizer to maintain a concentration of hydrogen peroxide in the wastewater in the vessel at 250 mg/L or more.
17. The system of claim 16, wherein the source of hydrogen peroxide includes a waste stream of the semiconductor manufacturing facility.
18. The system of claim 12, wherein the wastewater includes one or more anti-corrosives for copper and the system is configured to decompose the anti -corrosives for copper with hydroxyl radicals produced from the oxidizer with the copper acting as a catalyst from the production of the hydroxyl radicals.
19. The system of claim 12, wherein the wastewater includes one or more azole compounds and the system is configured to decompose the one or more azoles with hydroxyl radicals produced from the oxidizer with the copper acting as a catalyst from the production of the hydroxyl radicals.
20. The system of claim 12, wherein the wastewater includes one or more of 1,2,4- Triazole, IH-Benzotriazole pyrazole. Benzotriazole, 5-methyl IH-benzotriazole (Tolutriazole), or 3-amino 1,2,4-triazole and the system is configured to decompose the one or more of 1,2,4-Triazole, IH-Benzo triazole pyrazole, Benzotriazole, Tolutriazole, or 3- amino 1,2,4-triazole with hydroxyl radicals produced from the oxidizer with the copper acting as a catalyst from the production of the hydroxyl radicals.
21. The system of claim 12, wherein the source of w aste ater is a unit operation at the semiconductor manufacturing facility.
22. The system of claim 12, wherein the source of wastewater is a copper CMP operation at the semiconductor manufacturing facility.
23. The system of claim 12, wherein the source of copper includes a copper plating operation at the semiconductor manufacturing facility.
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