WO2011072492A1 - Chemical mechanical polishing liquid - Google Patents
Chemical mechanical polishing liquid Download PDFInfo
- Publication number
- WO2011072492A1 WO2011072492A1 PCT/CN2010/002063 CN2010002063W WO2011072492A1 WO 2011072492 A1 WO2011072492 A1 WO 2011072492A1 CN 2010002063 W CN2010002063 W CN 2010002063W WO 2011072492 A1 WO2011072492 A1 WO 2011072492A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- polishing liquid
- star
- liquid according
- group
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 67
- 239000007788 liquid Substances 0.000 title claims abstract description 41
- 239000000126 substance Substances 0.000 title claims abstract description 22
- 230000007797 corrosion Effects 0.000 claims abstract description 15
- 238000005260 corrosion Methods 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 239000003112 inhibitor Substances 0.000 claims abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 229920001577 copolymer Polymers 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 10
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- -1 ethylene, propylene, styrene Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 4
- 229940120146 EDTMP Drugs 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 150000007524 organic acids Chemical group 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 239000001263 FEMA 3042 Substances 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
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- 150000002923 oximes Chemical class 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000015523 tannic acid Nutrition 0.000 claims description 3
- 229940033123 tannic acid Drugs 0.000 claims description 3
- 229920002258 tannic acid Polymers 0.000 claims description 3
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 2
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 claims description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- RUSUZAGBORAKPY-UHFFFAOYSA-N acetic acid;n'-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCNCCN RUSUZAGBORAKPY-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 150000003863 ammonium salts Chemical group 0.000 claims description 2
- LOGBRYZYTBQBTB-UHFFFAOYSA-N butane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CC(O)=O LOGBRYZYTBQBTB-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 229940074391 gallic acid Drugs 0.000 claims description 2
- 235000004515 gallic acid Nutrition 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 claims description 2
- 229960003330 pentetic acid Drugs 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
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- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 claims 1
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- 150000002148 esters Chemical class 0.000 claims 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims 1
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- 239000004408 titanium dioxide Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 230000007547 defect Effects 0.000 abstract description 5
- 239000007769 metal material Substances 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
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- GDCRSXZBSIRSFR-UHFFFAOYSA-N ethyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCOC(=O)C=C GDCRSXZBSIRSFR-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 230000010354 integration Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 239000003002 pH adjusting agent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
Definitions
- the invention relates to a chemical mechanical polishing liquid
- the polished surface of the substrate is directly in contact with the rotating polishing pad while applying pressure on the back surface of the substrate.
- the polishing pad rotates with the stage while maintaining a downward force on the back side of the substrate, and a liquid composed of an abrasive and a chemically active solution (commonly referred to as a chemical mechanical polishing liquid) is applied to the polishing pad.
- the polishing liquid chemically reacts with the film being polished and mechanically starts the polishing process.
- Chemical mechanical polishing fluids are an important factor in CMP, and suitable chemical mechanical polishing fluids can be selected to change the polishing performance according to the needs of the process.
- a polishing fluid for aluminum containing abrasive particles, phosphoric acid and hydrogen peroxide, which has a high removal rate of aluminum, is disclosed in U.S. Patent No. 5,209,816.
- the present invention discloses a new chemical mechanical polishing liquid for polishing a metal layer.
- This polishing liquid can be formed by combining the following materials: abrasive particles, complexing agents, and corrosion inhibitors.
- the use of the slurry of the present invention can reduce the metal removal rate, prevent overall and local corrosion of the metal material, significantly reduce defects, and improve surface quality.
- a specific method of the present invention is to add a corrosion inhibitor to the polishing liquid.
- the corrosion inhibitor is a polymer surfactant having a star structure
- the chemical mechanical polishing liquid characterized in that the pigment affinity group is one or more of a hydroxyl group, an amino group and a carboxyl group.
- the polymerizable monomer forming the star-shaped polymer containing the pigment-affinity group includes one or more of the following: an acrylic monomer, an acrylate monomer, an acrylamide monomer, and an epoxy acetamidine. .
- the acrylic monomer is acrylic acid and/or methacrylic acid; the acrylate monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, A One or more of propyl acrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate; the acrylamide monomer is acrylamide and/or Methacrylamide.
- the monomer forming the star polymer containing the pigment-affinity group also includes other vinyl monomers.
- the other vinyl monomer is ethylene, propylene, styrene or p-methylstyrene.
- the star polymer containing the pigment affinity group is a polyacrylic acid star homopolymer, a binary star copolymer of styrene and hydroxyethyl acrylate, and two of methyl p-styrene and ethylene oxide.
- Metastar copolymer binary star copolymer of styrene and epoxy oxime, binary star copolymer of methyl methacrylate and epoxy oxime, binary of methyl acrylate and hydroxyethyl acrylate Star copolymer, acrylic acid and acrylic acid A binary star copolymer of hydroxyethyl enoate, and one or more of a trivalent star copolymer of acrylic acid, butyl acrylate and acrylamide.
- the star polymer containing the pigment-affinity group has a number average molecular weight of 800 to 50,000.
- the content of the star-type polymer containing the pigment-affinity group is 0.0001 to 5% by mass.
- the abrasive particles are one or more of silica, alumina, silica, aluminum-coated silica, ceria, titania and polymer abrasive particles.
- the content of the abrasive particles is 0.1 to 20% by mass.
- the abrasive particles have a particle diameter of 20 to 150 nm.
- the complexing agent is an organic acid and a salt thereof, an organic phosphonic acid and a salt thereof.
- the organic acid is acetic acid, oxalic acid, citric acid, tartaric acid, malonic acid, succinic acid, maleic acid, malic acid, lactic acid, tannic acid, gallic acid and sulfosalicylic acid, ethylenediaminetetraacetic acid.
- organic phosphonic acid is 2-phosphonic acid butane-1 , 2, 4-tricarboxylic acid, aminotrimethylene phosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylene phosphonic acid, diethylenetriamine pentamethylphosphonic acid, polyol phosphonate, 2-hydroxyl
- phosphonic acid acetic acid, ethylenediaminetetramethylene phosphonic acid, and polyaminopolyether methylphosphonic acid is an ammonium salt, a potassium salt, a sodium salt or the like.
- the content of the complexing agent is 0.01% to 10 % by mass.
- the chemical mechanical polishing liquid of the present invention may further comprise an oxidizing agent.
- the oxidizing agent can be any oxidizing agent in the prior art, preferably hydrogen peroxide, ferric nitrate, organic peroxides and/or inorganic peroxides.
- the chemical mechanical polishing liquid of the present invention may further include a surfactant, a viscosity modifier, a pH adjuster, and the like.
- Another object of the present invention is to provide the use of the chemical mechanical polishing liquid of the present invention in polishing a metal, which is aluminum, copper, tantalum, tantalum nitride, titanium, titanium nitride, silver or gold, preferably polished aluminum.
- the positive progress of the present invention is that the chemical mechanical polishing liquid of the present invention can significantly reduce the defect rate, increase the level of planarization of the metal surface, and significantly reduce the polishing rate of the metal.
- Table 1 shows Examples 1 to 30 of the chemical mechanical polishing liquid of the present invention. According to the formulation given in the table, all the components were uniformly mixed, and the mass percentage was made up to 100% with water. Adjust to the desired pH with KOH or HNO 3 .
- Table 2 shows the comparative polishing liquid 1 and the polishing liquid of the present invention, and according to the formulation given in the table, the mass percentage is made up to 100% with water, and adjusted to the desired pH value with KOH or HNO 3 . Mix well.
- the blank aluminum wafer was polished using the comparative polishing liquid 1 and the polishing liquids 31 to 36 of the present invention, and the decanting rate is shown in Table 3.
- the aluminum wafer was immersed in the polishing solution for 30 minutes, and the static corrosion rate of aluminum was measured. See Table 3.
- Polishing material Empty aluminum wafer; Polishing conditions: Downforce 3Psi, Polishing disc and polishing head speed 70/80rpm, polishing pad PPG MX710, polishing liquid flow rate 100ml/min, polishing machine for Logitech PM5 Polisher
- Table 3 compares the removal rate of metal aluminum by polishing solution 1 and polishing solution 3 ⁇ 36
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
A chemical mechanical polishing liquid for metal can be formed by combining the following substances: abrasive particles, a complexing agent and a corrosion inhibitor. By using the polishing liquid, the removal rate of metal is reduced and the overall or partial corrosion on the metal material is prevented, therefore evidently reducing defects and improving the surface quality.
Description
一种化学机械抛光液 Chemical mechanical polishing liquid
技术领域 Technical field
本发明涉及一种化学机械抛光液 The invention relates to a chemical mechanical polishing liquid
技术背景 technical background
随着微电子技术的发展，甚大规模集成电路芯片集成度已高达几十亿个 元器件， 特征尺寸已进入纳米级， 这就要求微电子工艺中的近百道工艺， 尤 其是多层布线、 衬底、 介质必须进行化学机械全局平整化， 而化学机械抛光 With the development of microelectronics technology, the integration of very large-scale integrated circuit chips has reached several billion components, and the feature size has entered the nanometer level. This requires nearly one hundred processes in the microelectronics process, especially multilayer wiring and lining. The bottom and the medium must be chemically mechanically planarized, while chemical mechanical polishing
(CMP) 已被证明是最好的平整化方法。 (CMP) has proven to be the best method of planarization.
在化学机械抛光方法中， 将基底的被抛光表面直接与旋转抛光垫接触， 同时在基底背面施加压力。 在抛光期间， 抛光垫随操作台旋转， 同时在基底 背面保持向下的力， 将磨料和化学活性溶液组成的液体（通常称为化学机械 抛光液）涂布于抛光垫片上， 该化学机械抛光液与正在抛光的薄膜发生化学 反应和机械作用开始进行抛光过程。 化学机械抛光液在 CMP中是一种重要 的,因素，而可根据制程的需要来选取合适的化学机械抛光液的来改变抛光性 能。 In the chemical mechanical polishing method, the polished surface of the substrate is directly in contact with the rotating polishing pad while applying pressure on the back surface of the substrate. During polishing, the polishing pad rotates with the stage while maintaining a downward force on the back side of the substrate, and a liquid composed of an abrasive and a chemically active solution (commonly referred to as a chemical mechanical polishing liquid) is applied to the polishing pad. The polishing liquid chemically reacts with the film being polished and mechanically starts the polishing process. Chemical mechanical polishing fluids are an important factor in CMP, and suitable chemical mechanical polishing fluids can be selected to change the polishing performance according to the needs of the process.
在典型的金属化学机械抛光中， 缺陷水平通常较高， 尤其是存在点蚀、 边蚀、 腐蚀等问题。 而且， 抛光速率也很高， 对金属表面的损伤程度较大， 易产生如划伤、 表面粗糙等问题。 如美国专利 US5, 209,816揭示了一种用于 铝的抛光液， 其含有研磨颗粒、 磷酸和双氧水， 铝的去除速率较高。 In typical metal chemical mechanical polishing, the level of defects is usually high, especially in the presence of pitting, edge etching, corrosion, and the like. Moreover, the polishing rate is also high, and the degree of damage to the metal surface is large, which is liable to cause problems such as scratches and rough surfaces. A polishing fluid for aluminum containing abrasive particles, phosphoric acid and hydrogen peroxide, which has a high removal rate of aluminum, is disclosed in U.S. Patent No. 5,209,816.
确认本
发明概要 本发明的目的是提供一种降低金属的去除速率， 防止金属材料在酸性条 件下的整体和局部腐蚀， 减少缺陷， 提高表面质量的化学机械抛光液。 本发明揭示了一新的用于抛光金属层的化学机械抛光液。这种抛光液可 以通过下列物质组合在一起而形成： 研磨颗粒、 络合剂及腐蚀抑制剂。 使用 本发明的浆料的可以降低金属的去除速率， 防止金属材料的整体和局部腐 蚀， 使缺陷明显下降， 提高表面质量。 详细说来， 本发明的具体方法是向抛光液中添加了腐蚀抑制剂。 该腐蚀抑制剂是一种具有星型结构的聚合物表面活性剂 Confirmation SUMMARY OF THE INVENTION It is an object of the present invention to provide a chemical mechanical polishing liquid which reduces the metal removal rate, prevents overall and local corrosion of metallic materials under acidic conditions, reduces defects, and improves surface quality. The present invention discloses a new chemical mechanical polishing liquid for polishing a metal layer. This polishing liquid can be formed by combining the following materials: abrasive particles, complexing agents, and corrosion inhibitors. The use of the slurry of the present invention can reduce the metal removal rate, prevent overall and local corrosion of the metal material, significantly reduce defects, and improve surface quality. In detail, a specific method of the present invention is to add a corrosion inhibitor to the polishing liquid. The corrosion inhibitor is a polymer surfactant having a star structure
所述的化学机械抛光液， 其特征在于： 所述的颜料亲和基团为羟基、 氨 基和羧基中的一种或多种。 The chemical mechanical polishing liquid characterized in that the pigment affinity group is one or more of a hydroxyl group, an amino group and a carboxyl group.
形成所述的含颜料亲和基团的星型聚合物的聚合单体包括下列中的一 种或多种： 丙烯酸类单体、 丙烯酸酯类单体、 丙烯酰胺类单体和环氧乙垸。 The polymerizable monomer forming the star-shaped polymer containing the pigment-affinity group includes one or more of the following: an acrylic monomer, an acrylate monomer, an acrylamide monomer, and an epoxy acetamidine. .
所述的丙烯酸类单体为丙烯酸和 /或甲基丙烯酸；所述的丙烯酸酯类单体 为丙烯酸甲酯、 甲基丙烯酸甲酯、 丙烯酸乙酯、 甲基丙烯酸乙酯、 丙烯酸丙 酯、 甲基丙烯酸丙酯、 丙烯酸丁酯、 甲基丙烯酸丁酯、 丙炼酸羟乙酯和甲基 丙烯酸羟乙酯中的一种或多种;所述的丙烯酰胺类单体为丙烯酰胺和 /或甲基 丙烯酰胺。 The acrylic monomer is acrylic acid and/or methacrylic acid; the acrylate monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, A One or more of propyl acrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate; the acrylamide monomer is acrylamide and/or Methacrylamide.
形成所述的含颜料亲和基团的星型聚合物的单体还包括其他乙烯基类 单体。 The monomer forming the star polymer containing the pigment-affinity group also includes other vinyl monomers.
所述的其他乙烯基类单体为乙烯、 丙烯、 苯乙烯或对甲基苯乙烯。 所述的含颜料亲和基团的星型聚合物为聚丙烯酸星型均聚物，苯乙烯与 丙烯酸羟乙酯的二元星型共聚物，对甲基苯乙烯与环氧乙烷的二元星型共聚 物， 苯乙烯与环氧乙垸的二元星型共聚物， 甲基丙烯酸甲酯与环氧乙垸的二 元星型共聚物， 丙烯酸甲酯与丙烯酸羟乙酯的二元星型共聚物， 丙烯酸与丙
烯酸羟乙酯的二元星型共聚物， 以及丙烯酸、 丙烯酸丁酯和丙烯酰胺的三元 星型共聚物中的一种或多种。 The other vinyl monomer is ethylene, propylene, styrene or p-methylstyrene. The star polymer containing the pigment affinity group is a polyacrylic acid star homopolymer, a binary star copolymer of styrene and hydroxyethyl acrylate, and two of methyl p-styrene and ethylene oxide. Metastar copolymer, binary star copolymer of styrene and epoxy oxime, binary star copolymer of methyl methacrylate and epoxy oxime, binary of methyl acrylate and hydroxyethyl acrylate Star copolymer, acrylic acid and acrylic acid A binary star copolymer of hydroxyethyl enoate, and one or more of a trivalent star copolymer of acrylic acid, butyl acrylate and acrylamide.
所述的含颜料亲和基团的星型聚合物的数均分子量为 800-50000。 所述的含颜料亲和基团的星型聚合物的含量为质量百分比 0.0001~5%。 所述的研磨颗粒为二氧化硅、 三氧化二铝、 惨杂铝的二氧化硅、 覆盖铝 的二氧化硅、 二氧化铈、 二氧化钛和高分子研磨颗粒中的一种或多种。 所述 的研磨颗粒的含量为质量百分比 0.1 ~20%。 所述的研磨颗粒的粒径为 20〜150nm。 所述络合剂为有机酸及其盐、 有机膦酸及其盐。 The star polymer containing the pigment-affinity group has a number average molecular weight of 800 to 50,000. The content of the star-type polymer containing the pigment-affinity group is 0.0001 to 5% by mass. The abrasive particles are one or more of silica, alumina, silica, aluminum-coated silica, ceria, titania and polymer abrasive particles. The content of the abrasive particles is 0.1 to 20% by mass. The abrasive particles have a particle diameter of 20 to 150 nm. The complexing agent is an organic acid and a salt thereof, an organic phosphonic acid and a salt thereof.
所述的有机酸为醋酸、 草酸、 柠檬酸、 酒石酸、 丙二酸、 丁二酸、 马来 酸、 苹果酸、 乳酸、 丹宁酸、 没食子酸和磺基水杨酸、 乙二胺四乙酸、 环己 垸四乙酸、 乙二胺二琥珀酸、 二乙烯三胺五乙酸和三乙烯四胺六乙酸中的一 种或多种；所述的有机膦酸为 2-膦酸丁烷 -1， 2， 4-三羧酸、氨基三甲叉膦酸、 羟基乙叉二膦酸、 乙二胺四甲叉膦酸、 二乙烯三胺五甲叉膦酸、 多元醇膦酸 酯、 2-羟基膦酸基乙酸、 乙二胺四甲叉膦酸和多氨基多醚基甲叉膦酸中的一 种或多种。 所述的盐为铵盐、 钾盐和钠盐等。 所述络合剂的含量为质量百分 比 0.01〜10%0 The organic acid is acetic acid, oxalic acid, citric acid, tartaric acid, malonic acid, succinic acid, maleic acid, malic acid, lactic acid, tannic acid, gallic acid and sulfosalicylic acid, ethylenediaminetetraacetic acid. And one or more of cyclohexyltetraacetic acid, ethylenediamine disuccinic acid, diethylenetriaminepentaacetic acid and triethylenetetramine hexaacetic acid; said organic phosphonic acid is 2-phosphonic acid butane-1 , 2, 4-tricarboxylic acid, aminotrimethylene phosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylene phosphonic acid, diethylenetriamine pentamethylphosphonic acid, polyol phosphonate, 2-hydroxyl One or more of phosphonic acid acetic acid, ethylenediaminetetramethylene phosphonic acid, and polyaminopolyether methylphosphonic acid. The salt is an ammonium salt, a potassium salt, a sodium salt or the like. The content of the complexing agent is 0.01% to 10 % by mass.
本发明的化学机械抛光液还可以包含氧化剂。该氧化剂可为现有技术中 的任何氧化剂， 较佳地为过氧化氢、硝酸铁、有机过氧化物和 /或无机过氧化 物。 The chemical mechanical polishing liquid of the present invention may further comprise an oxidizing agent. The oxidizing agent can be any oxidizing agent in the prior art, preferably hydrogen peroxide, ferric nitrate, organic peroxides and/or inorganic peroxides.
本发明的化学机械抛光液还可以包括表面活性剂、 粘度调节剂、 pH调 节剂等。 本发明的另一目的是提供本发明的化学机械抛光液在抛光金属中的用 途， 所述的金属为铝、 铜、 钽、 氮化钽、 钛、 氮化钛、 银或金， 优选抛光铝。
本发明的积极进步效果在于：本发明的化学机械抛光液可以明显降低缺 陷率， 提高金属表面平坦化水平， 显著地降低金属的抛光速率。 The chemical mechanical polishing liquid of the present invention may further include a surfactant, a viscosity modifier, a pH adjuster, and the like. Another object of the present invention is to provide the use of the chemical mechanical polishing liquid of the present invention in polishing a metal, which is aluminum, copper, tantalum, tantalum nitride, titanium, titanium nitride, silver or gold, preferably polished aluminum. . The positive progress of the present invention is that the chemical mechanical polishing liquid of the present invention can significantly reduce the defect rate, increase the level of planarization of the metal surface, and significantly reduce the polishing rate of the metal.
发明内容 Summary of the invention
下面用实施例来进一步说明本发明， 但本发明并不受其限制。 The invention is further illustrated by the following examples, but the invention is not limited thereto.
实施例 1~30 Example 1~30
表 1给出了本发明的化学机械抛光液的实施例 1〜30， 按表中所给配方， 将所有组分混合均匀， 用水补足质量百分比至 100%。 用 KOH或 HN03调 节到所需要的 pH值。 Table 1 shows Examples 1 to 30 of the chemical mechanical polishing liquid of the present invention. According to the formulation given in the table, all the components were uniformly mixed, and the mass percentage was made up to 100% with water. Adjust to the desired pH with KOH or HNO 3 .
表 1 实施例 1〜30 Table 1 Example 1~30
23 4 SiO2(80nm) 1 0.001 星形聚丙烯酸， Mn=10000 5 二乙烯三胺 丙烯酸乙酯与丙烯酰胺的星23 4 SiO 2 (80nm) 1 0.001 star polyacrylic acid, Mn = 10000 5 diethylene triamine ethyl acrylate and acrylamide star
24 3 SiO2(80nm) 1 五乙酸 0.0015 形共聚物， Mn=8000 4 对甲基苯乙烯与环氧乙垸的24 3 SiO 2 (80nm) 1 pentaacetic acid 0.0015 copolymer, Mn=8000 4 p-methylstyrene and epoxy acetamidine
25 3 SiO2(50nm) 7 草酸 0.5 二元星型共聚物， Mn=6000 4 25 3 SiO 2 (50nm) 7 Oxalic acid 0.5 binary star copolymer, Mn=6000 4
2-膦酸丁垸基 苯乙烯与环氧乙垸的二元星 Binary star of 2-butylphosphonate and styrene
26 6 SiO2(50nm) 1 0.1 型共聚物， Mn=8000 4 掺 杂 铝 的 甲基丙烯酸丁酯和丙烯酸的26 6 SiO 2 (50nm) 1 0.1 type copolymer, Mn=8000 4 doped aluminum butyl methacrylate and acrylic acid
27 6 SiO2(20nm) 3 丹宁酸 0.005 星形共聚物， Mn=12000 5 聚甲基丙烯酸 甲基丙烯酸乙酯和丙烯酸的27 6 SiO 2 (20nm) 3 tannic acid 0.005 star copolymer, Mn=12000 5 polyethyl methacrylate ethyl acrylate and acrylic acid
28 5 甲酯 (150nm) 5 马来酸 0.015 星形共聚物， Mn=6000 5 聚 苯 乙 烯 三乙烯四胺 苯乙烯与环氧乙垸的二元星28 5 methyl ester (150nm) 5 maleic acid 0.015 star copolymer, Mn=6000 5 polystyrene ethylene triethylenetetramine binary star of styrene and epoxy acetam
29 20 (120nm) 5 0.002 型共聚物， Mn=10000 5 丙烯酸羟乙酯与丙烯酰胺的29 20 (120nm) 5 0.002 type copolymer, Mn = 10000 5 hydroxyethyl acrylate and acrylamide
2 草酸铰 0.8 星形共聚物， Mn=3000 2 oxalic acid hinge 0.8 star copolymer, Mn=3000
30. 3 SiO2(50nm) 氧化剂 1%双氧水 0.2 星形聚丙烯酸， Mn=3000 4 30. 3 SiO 2 (50nm) oxidant 1% hydrogen peroxide 0.2 star polyacrylic acid, Mn=3000 4
效果实施例 Effect embodiment
表 2给出了对比抛光液 1和本发明的抛光液， 按表中所给配方， 用水补 足质量百分比至 100%，用 KOH或 HN03调节到所需要的 pH值。混合均匀 即可。 Table 2 shows the comparative polishing liquid 1 and the polishing liquid of the present invention, and according to the formulation given in the table, the mass percentage is made up to 100% with water, and adjusted to the desired pH value with KOH or HNO 3 . Mix well.
对比抛光液 1和抛光液 Contrast polishing solution 1 and polishing solution
研磨颗粒 络合剂 星型聚合物 抛光液 具体物 pH Abrasive particles complexing agent star polymer polishing liquid concrete pH
'含量 wt% 含量 t% 含量 'Content wt% content t% content
具体物质 具体物质 Specific substance
质 wt% Quality wt%
Si02 Si0 2
对比1 2 0.5 草酸 \ 3 Compare 1 2 0.5 oxalic acid \ 3
(70nm) (70nm)
甲基丙烯酸丁酯、 Butyl methacrylate,
Si02 丙烯酸羟乙酯和苯 Si0 2 hydroxyethyl acrylate and benzene
31 2 0.5 草酸 0.01 3 31 2 0.5 Oxalic acid 0.01 3
( 70nm) 乙烯的三元星形共 (70nm) ethylene ternary star
聚物， Mn=3000 Polymer, Mn=3000
甲基丙烯酸丁酯、 Butyl methacrylate,
Si02 丙烯酸羟乙酯和苯 Si0 2 hydroxyethyl acrylate and benzene
32 2 0.5 草酸 0.1 3 . 32 2 0.5 oxalic acid 0.1 3 .
(70nm) 乙烯的三元星形共 (70nm) ethylene ternary star
聚物， Mn=3000
甲基丙烯酸丁酯、 Polymer, Mn=3000 Butyl methacrylate,
Si02 丙烯酸羟乙酯和苯 Si0 2 hydroxyethyl acrylate and benzene
33 2 0.5 草酸 0.5 3 33 2 0.5 oxalic acid 0.5 3
( 70nm) 乙烯的三元星形共 (70nm) ethylene ternary star
聚物， Mn=3000 Polymer, Mn=3000
丙烯酸羟乙酯、 丙 Hydroxyethyl acrylate, C
Si02 乙二胺 Si0 2 ethylene diamine
34 2 0.5 烯酸的 34 2 0.5 olefinic acid
四甲叉 0.005 烯酰胺和丙 3 ( 70nm) 三元星形共聚物 Tetramethylidene 0.005 enamide and C 3 (70 nm) ternary star copolymer
膦酸 Phosphonic acid
Mn=5000 Mn=5000
Si02 丙烯酸乙酯与丙烯 Si0 2 ethyl acrylate and propylene
35 2 0.5 马来酸 0.05 酰胺的星形共聚物 4 35 2 0.5 maleic acid 0.05 amide star copolymer 4
(70nm) (70nm)
Mn=5000 Mn=5000
苯乙烯与丙烯酸羟 Styrene and hydroxy acrylate
Si02 0.1 乙酯的二元星形共 Binary star of Si0 2 0.1 ethyl ester
乙二胺 Ethylenediamine
36 2 0.5 聚物 Mn=6000 4 36 2 0.5 Polymer Mn=6000 4
(70nm) 四乙酸 (70nm) tetraacetic acid
0.001 星形聚丙烯酸 0.001 star polyacrylic acid
Mn=3000 Mn=3000
采用对比抛光液 1和本发明的抛光液 31〜36对空片铝晶片进行抛光， 去赊速率见表 3。将铝晶片在抛光液中浸泡 30分钟，测得铝的静态腐蚀速率 见表.3 The blank aluminum wafer was polished using the comparative polishing liquid 1 and the polishing liquids 31 to 36 of the present invention, and the decanting rate is shown in Table 3. The aluminum wafer was immersed in the polishing solution for 30 minutes, and the static corrosion rate of aluminum was measured. See Table 3.
：抛光材料： 空片铝晶片； 抛光条件： 下压力 3Psi， 抛光盘及抛光头转速 70/80rpm,抛光垫 PPG MX710,抛光液流速 100ml/min，抛光机台为 Logitech PM5 Polisher : Polishing material: Empty aluminum wafer; Polishing conditions: Downforce 3Psi, Polishing disc and polishing head speed 70/80rpm, polishing pad PPG MX710, polishing liquid flow rate 100ml/min, polishing machine for Logitech PM5 Polisher
表 3对比抛光液 1和抛光液 3ί〜36对金属铝的去除速率 Table 3 compares the removal rate of metal aluminum by polishing solution 1 and polishing solution 3 ί~36
和铝的静态腐蚀速率 And aluminum static corrosion rate
抛光液 铝的去除速率 （A/min ) 铝的静态腐蚀速率 （A/min) 对比 1 1242 3. 76 Polishing fluid Aluminum removal rate (A/min) Static corrosion rate of aluminum (A/min) Comparison 1 1242 3. 76
31 549 1. 65 31 549 1. 65
32 151 0. 68 32 151 0. 68
33 67 0 33 67 0
34 780 1. 97 34 780 1. 97
35 413 1. 20 35 413 1. 20
36 249 0. 73
由表可见， 使用本发明的抛光液， 可大大降低铝的去除速率， 同时铝 的静态腐蚀速率也降低， 能有效的抑制腐蚀。
36 249 0. 73 It can be seen from the table that the use of the polishing liquid of the present invention can greatly reduce the removal rate of aluminum, and at the same time, the static corrosion rate of aluminum is also lowered, and the corrosion can be effectively suppressed.
Claims
1、 一种化学机械抛光液， 其包含： 研磨颗粒、 络合剂及腐蚀抑制剂。A chemical mechanical polishing liquid comprising: abrasive particles, a complexing agent, and a corrosion inhibitor.
2、 如权利要求 1所述抛光液， 其特征在于， 所述腐蚀抑制剂为含颜料 亲和基团的星型聚合物。 The polishing liquid according to claim 1, wherein the corrosion inhibitor is a star-shaped polymer containing a pigment-affinity group.
3、 如权利要求 2所述抛光液， 其特征在于， 所述含颜料亲和基团的星 型聚合物为选自羟基、 氨基和羧基中的一种或多种。 The polishing liquid according to claim 2, wherein the star-containing polymer having a pigment-affinity group is one or more selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group.
4、 如权利要求 3所述抛光液， 其特征在于， 形成所述的含颜料亲和基 团的星型聚合物的聚合单体包括下列中的一种或多种： 丙烯酸类单体、 丙烯 酸酯类单体、 丙烯酰胺类单体和环氧乙垸。 4. The polishing liquid according to claim 3, wherein the polymerizable monomer forming the star-shaped polymer containing the pigment-affinity group comprises one or more of the following: an acrylic monomer, acrylic acid Ester monomers, acrylamide monomers and epoxy acetam.
5、 如权利要求 4所述抛光液， 其特征在于， 所述的丙烯酸类单体为丙 烯酸和 /或甲基丙烯酸；所述的丙烯酸酯类单体为选自丙烯酸甲酯、甲基丙烯 酸甲:酯、 丙烯酸乙酯、 甲基丙烯酸乙酯、 丙烯酸丙酯、 甲基丙烯酸丙酯、 丙 烯酸丁酯、 甲基丙烯酸丁酯、 丙烯酸羟乙酯和甲基丙烯酸羟乙酯中的一种或 多种； 所述的丙烯酰胺类单体为丙烯酰胺和 /或甲基丙烯酰胺。 The polishing liquid according to claim 4, wherein the acrylic monomer is acrylic acid and/or methacrylic acid; and the acrylate monomer is selected from the group consisting of methyl acrylate and methacrylic acid. : one or more of ester, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate The acrylamide monomer is acrylamide and/or methacrylamide.
6、 如权利要求 4所述抛光液， 其特征在于， 形成所述的含颜料亲和基 团的星型聚合物的单体还包括其他乙烯基类单体。 The polishing liquid according to claim 4, wherein the monomer forming the star-shaped polymer containing the pigment-affinity group further comprises other vinyl-based monomers.
7、 如权利要求 6所述抛光液， 其特征在于， 所述其他乙烯基类单体为 选自乙烯、 丙烯、 苯乙烯和对甲基苯乙烯中的一种或多种。 The polishing liquid according to claim 6, wherein the other vinyl monomer is one or more selected from the group consisting of ethylene, propylene, styrene, and p-methylstyrene.
8、 如权利要求 2所述抛光液， 其特征在于， 所述含颜料亲和基团的星 型聚合物为选自聚丙烯酸星型均聚物，苯乙烯与丙烯酸羟乙酯的二元星型共 聚物， 对甲基苯乙烯与环氧乙烷的二元星型共聚物， 苯乙烯与环氧乙烷的二 元星型共聚物， 甲基丙烯酸甲酯与环氧乙垸的二元星型共聚物， 丙烯酸甲酯 与丙烯酸羟乙酯的二元星型共聚物，丙烯酸与丙烯酸羟乙酯的二元星型共聚 物，以及丙烯酸、丙烯酸丁酯和丙烯酰胺的三元星型共聚物中的一种或多种。 8. The polishing liquid according to claim 2, wherein the star-shaped polymer containing a pigment-affinity group is a binary star selected from the group consisting of polyacrylic acid star homopolymer, styrene and hydroxyethyl acrylate. Copolymer, binary star copolymer of p-methylstyrene and ethylene oxide, binary star copolymer of styrene and ethylene oxide, binary of methyl methacrylate and epoxy oxime Star copolymer, binary star copolymer of methyl acrylate and hydroxyethyl acrylate, binary star copolymer of acrylic acid and hydroxyethyl acrylate, and ternary star copolymerization of acrylic acid, butyl acrylate and acrylamide One or more of the substances.
9、 如权利要求 2所述抛光液， 其特征在于， 所述含颜料亲和基团的星 型聚合物的数均分子量为 800-50000。 The polishing liquid according to claim 2, wherein the star-type polymer having a pigment-affinity group has a number average molecular weight of 800 to 50,000.
10、 如权利要求 2所述抛光液， 其特征在于， 所述含颜料亲和基团的星 型聚合物的含量为质量百分比 0.0001〜5%。 The polishing liquid according to claim 2, wherein the content of the star-containing polymer containing the pigment-affinity group is 0.0001 to 5% by mass.
11、 如权利要求 1所述抛光液， 其特征在于， 所述研磨颗粒为选自二氧 化硅、 三氧化二铝、 掺杂铝的二氧化硅、 覆盖铝的二氧化硅、 二氧化铈、 二 氧化钛和高分子研磨颗粒中的一种或多种。 The polishing liquid according to claim 1, wherein the abrasive particles are selected from the group consisting of silica, alumina, aluminum-doped silica, aluminum-covered silica, and cerium oxide. One or more of titanium dioxide and polymer abrasive particles.
12、 如权利要求 1所述抛光液， 其特征在于， 所述研磨颗粒的含量为质 量百分比 0.1〜20%。 The polishing liquid according to claim 1, wherein the abrasive particles are contained in an amount of 0.1 to 20% by mass.
13、 如权利要求 1 所述抛光液， 其特征在于， 所述研磨颗粒的粒径为 20~150nm。 The polishing liquid according to claim 1, wherein the abrasive particles have a particle diameter of 20 to 150 nm.
14、 如权利要求 1所述的抛光液， 其特征在于， 所述络合剂为有机酸及 其盐、 有机膦酸及其盐。 The polishing liquid according to claim 1, wherein the complexing agent is an organic acid and a salt thereof, an organic phosphonic acid, and a salt thereof.
15、 如权利要求 14所述的抛光液， 其特征在于， 所述有机酸为选自醋 酸、 草酸、 柠檬酸、 酒石酸、 丙二酸,、 丁二酸、 马来酸、 苹果酸、 乳酸、 丹 宁酸、 没食子酸、 磺基水杨酸、 乙二胺四乙酸、 环己垸四乙酸、 乙二胺二琥 珀酸、 二乙烯三胺五乙酸和三乙烯四胺六乙酸中的一种或多种; 所述有机膦 酸为选自 2-膦酸丁烷 -1， 2， 4-三羧酸、 氨基三甲叉膦酸、 羟基乙叉二膦酸、 乙二胺四甲叉膦酸、 二乙烯三胺五甲叉膦酸、 多元醇膦酸酯、 2-羟基膦酸基 乙酸、 乙二胺四甲叉膦酸和多氨基多醚基甲叉膦酸中的一种或多种。所述的 盐为铵盐、 钾盐和 /或钠盐。 The polishing liquid according to claim 14, wherein the organic acid is selected from the group consisting of acetic acid, oxalic acid, citric acid, tartaric acid, malonic acid, succinic acid, maleic acid, malic acid, and lactic acid. One of tannic acid, gallic acid, sulfosalicylic acid, ethylenediaminetetraacetic acid, cyclohexyltetraacetic acid, ethylenediamine disuccinic acid, diethylenetriaminepentaacetic acid, and triethylenetetramine hexaacetic acid or a plurality of; the organic phosphonic acid is selected from the group consisting of 2-phosphonic acid butane-1, 2, 4-tricarboxylic acid, aminotrimethylene phosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediamine tetramethylene phosphonic acid, One or more of diethylenetriamine pentamethylphosphonic acid, polyol phosphonate, 2-hydroxyphosphonic acid acetic acid, ethylenediaminetetramethylene phosphonic acid, and polyaminopolyether methylphosphonic acid. The salt is an ammonium salt, a potassium salt and/or a sodium salt.
16、 如权利要求 1所述的抛光液， 其特征在于， 所述络合剂的含量为质 量百分比 0.01〜10%。 The polishing liquid according to claim 1, wherein the complexing agent is contained in an amount of 0.01 to 10% by mass.
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| CN102796458B (en) * | 2012-07-17 | 2014-04-23 | 清华大学 | Chemical mechanical polishing aqueous composite and chemical mechanical polishing process of titanium substrate |
| CN102876819B (en) * | 2012-10-16 | 2014-06-25 | 四川大学 | Ammonia-free softening additive and application thereof in leather softening process |
| CN103725256A (en) * | 2013-12-31 | 2014-04-16 | 上海集成电路研发中心有限公司 | Grinding particle system and polishing liquid for CMP (Chemical Mechanical Polishing) |
| CN104342704A (en) * | 2014-10-20 | 2015-02-11 | 苏州大学 | Oxidizing agent-free alkaline aluminum alloy polishing liquid and preparation method thereof |
| CN104388937B (en) * | 2014-11-03 | 2017-01-25 | 西南石油大学 | Chemical polishing solution for aluminum alloy frosted exterior trimming parts and application of chemical polishing solution |
| CN108251844B (en) * | 2018-03-29 | 2020-03-10 | 山西银光华盛镁业股份有限公司 | Bright treatment liquid for magnesium alloy die castings |
| CN111020590A (en) * | 2019-11-25 | 2020-04-17 | 昆山兰博旺新材料技术服务有限公司 | Environment-friendly aluminum alloy chemical polishing solution |
| CN115928073A (en) * | 2022-11-28 | 2023-04-07 | 广东红日星实业有限公司 | Grinding fluid and preparation method and application thereof |
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| CN1644640A (en) * | 2003-12-19 | 2005-07-27 | Cmp罗姆和哈斯电子材料控股公司 | Compositions and methods for controlled polishing of copper |
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