CN116948531A - Integrated circuit copper chemical mechanical polishing composition and preparation method and application thereof - Google Patents
Integrated circuit copper chemical mechanical polishing composition and preparation method and application thereof Download PDFInfo
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- CN116948531A CN116948531A CN202310523057.9A CN202310523057A CN116948531A CN 116948531 A CN116948531 A CN 116948531A CN 202310523057 A CN202310523057 A CN 202310523057A CN 116948531 A CN116948531 A CN 116948531A
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- Prior art keywords
- cerium
- polishing composition
- copper
- grinding
- acid
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- 238000005498 polishing Methods 0.000 title claims abstract description 136
- 239000010949 copper Substances 0.000 title claims abstract description 99
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 95
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 239000000126 substance Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 104
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 102
- 238000000227 grinding Methods 0.000 claims abstract description 88
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 239000002738 chelating agent Substances 0.000 claims abstract description 13
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 60
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 59
- 238000002156 mixing Methods 0.000 claims description 58
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 49
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 claims description 48
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 claims description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 34
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 34
- 229920000058 polyacrylate Polymers 0.000 claims description 32
- 239000000908 ammonium hydroxide Substances 0.000 claims description 31
- 239000004471 Glycine Substances 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 18
- DPUCLPLBKVSJIB-UHFFFAOYSA-N cerium;tetrahydrate Chemical compound O.O.O.O.[Ce] DPUCLPLBKVSJIB-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- 239000006228 supernatant Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 8
- 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 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 3
- 239000004472 Lysine Substances 0.000 claims description 3
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 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 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 235000019800 disodium phosphate Nutrition 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229960003330 pentetic acid Drugs 0.000 claims description 3
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 235000018977 lysine Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 74
- -1 cerium oxide compound Chemical class 0.000 abstract description 4
- 238000007517 polishing process Methods 0.000 abstract description 3
- RBZGEUJLKTVORU-UHFFFAOYSA-N 12014-84-5 Chemical compound [Ce]#[Si] RBZGEUJLKTVORU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 65
- 239000000243 solution Substances 0.000 description 60
- 239000000047 product Substances 0.000 description 44
- 238000000151 deposition Methods 0.000 description 43
- 150000000703 Cerium Chemical class 0.000 description 42
- 230000008021 deposition Effects 0.000 description 41
- 239000002002 slurry Substances 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000004576 sand Substances 0.000 description 30
- 238000001914 filtration Methods 0.000 description 29
- 238000012360 testing method Methods 0.000 description 28
- 238000003756 stirring Methods 0.000 description 27
- 239000010410 layer Substances 0.000 description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 18
- 239000010703 silicon Substances 0.000 description 18
- 229910052710 silicon Inorganic materials 0.000 description 18
- 239000000758 substrate Substances 0.000 description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 17
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 17
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical group [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 17
- 238000001354 calcination Methods 0.000 description 16
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 16
- 230000008569 process Effects 0.000 description 16
- 229910052721 tungsten Inorganic materials 0.000 description 16
- 238000000498 ball milling Methods 0.000 description 15
- SBLDRQWVOSCPAD-UHFFFAOYSA-K cerium(3+);carbonate;hydroxide Chemical compound [OH-].[Ce+3].[O-]C([O-])=O SBLDRQWVOSCPAD-UHFFFAOYSA-K 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- 238000001556 precipitation Methods 0.000 description 15
- 230000001105 regulatory effect Effects 0.000 description 15
- 229910021642 ultra pure water Inorganic materials 0.000 description 15
- 239000012498 ultrapure water Substances 0.000 description 15
- 238000001816 cooling Methods 0.000 description 14
- 239000012266 salt solution Substances 0.000 description 14
- 239000000725 suspension Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 238000009835 boiling Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 238000003825 pressing Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
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- 229940044927 ceric oxide Drugs 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- LJBTWTBUIINKRU-UHFFFAOYSA-K cerium(3+);triperchlorate Chemical compound [Ce+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LJBTWTBUIINKRU-UHFFFAOYSA-K 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent 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
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
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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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
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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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—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]
Abstract
The invention relates to the technical field of semiconductor integrated circuit manufacturing, in particular to an integrated circuit copper chemical mechanical polishing composition, a preparation method and application thereof. The polishing composition comprises the following raw materials in parts by weight: 3 to 5 parts of nano abrasive particles, 0.1 to 5.0 parts of high cerium oxide, 0.01 to 2.0 parts of metal complexing agent or metal chelating agent and 0.01 to 5.0 parts of surfactant. The invention uses high cerium as oxidant to replace the existing hydrogen peroxide, uses silicon oxide and cerium oxide compound as grinding particles, controls the silicon-cerium ratio to balance the grinding rate of the metal layer and the dielectric layer, and solves the dishing caused by unbalanced removal rate of copper and the dielectric layer in the existing copper interconnection chemical mechanical polishing process.
Description
Technical Field
The invention relates to the technical field of semiconductor integrated circuit manufacturing, in particular to an integrated circuit copper chemical mechanical polishing composition, a preparation method and application thereof.
Background
The 60-year history of integrated circuits (Integrated Circuit, IC) is a history of continuous development toward high integration, high density, high speed and high performance, and low energy consumption, so as to meet the application requirements of various fields such as computers, automotive electronics, satellite communications, electronic consumption, intelligent control, and the internet of things. According to moore's law, the number of transistors per unit area is doubled every 18 months, and the integration level of chips is over 100 hundred million at present, and the chip enters the ultra-large-scale integrated circuit (GLSI) era. In the process of shrinking transistor dimensions, various new processes, techniques, materials are continually introduced into integrated circuit fabrication in order to achieve smaller line widths. Today, the IC technology node has been stepped into the 3nm age, multilayer copper interconnection is an important technology in the process, the number of interconnection layers is up to more than 60 layers, and the total length of the interconnection line can reach 10 km.
As integrated circuit feature sizes continue to shrink, the gate delay requirements of the circuits become smaller. However, the RC delay of the conventional aluminum interconnect is relatively large, and the atomic stack formed in the interconnect line accompanying the atomic migration of the electron flow obstructs the electron flow, degrading the device reliability. To solve the above problems, IBM corporation in 1997 realized copper interconnect technology using a dual damascene process with copper metal material instead of conventional aluminum. Copper has a resistivity of 1.7 mu omega cm compared to aluminum, which is doubled lower than aluminum, which is advantageous for reducing RC delay. Meanwhile, in order to reduce the thickness of the interconnection layer, the low-K dielectric or the ultra-low-K dielectric is adopted to replace the traditional silicon dioxide for the intermetal insulating dielectric. The process reduces the distributed capacitance between the interconnection layers and the parasitic capacitance between the interconnection lines, thereby improving the working efficiency. In addition, copper has a higher melting point (1083 ℃) than aluminum (660 ℃) and can reduce the reliability problem caused by the electromigration phenomenon. So far, copper interconnection technology is developed rapidly and is a necessary process in the preparation process of integrated circuits. Although copper has a lower resistance than aluminum or tungsten, copper has a higher diffusion coefficient in silicon and tends to diffuse into the dielectric layer, so that it is common to deposit, for example, tantalum (Ta), tantalum nitride (TaN), titanium (Ti) or titanium nitride (TiN), cobalt (Co), ruthenium (Ru), etc., as diffusion barriers prior to depositing metallic copper on the sidewalls and bottom of the via.
The copper interconnect structure is completed by a dual damascene process (dual damascene) which can fill the trench and the wiring via simultaneouslyThe process is simple and the production efficiency is high. Etching a groove and a through hole in one or more dielectric layers on a substrate, then depositing metal in the groove and the through hole, and flattening the metal layer, the interlayer dielectric layer and the diffusion barrier layer by a CMP (chemical mechanical polishing) process, so that the surfaces of the metal layer and the dielectric layer are on the same plane. Fig. 1 is a schematic diagram of a typical copper interconnect damascene process. The chemical mechanical polishing (Chemical Mechanical Polishing, CMP) process is the only effective global planarization technique for integrated circuit fabrication and its principle is the interaction of mechanical polishing action and chemical etching action of the polishing liquid (slurry). The mechanism of action is generally believed that metallic copper is first oxidized to monovalent or divalent copper ions and then removed by mechanical action of abrasive particles, which cycle back and forth to planarize. The polishing liquid for CMP contains abrasive particles such as silicon oxide SiO 2 CeO of cerium oxide 2 Zirconium oxide ZrO 2 Alumina Al 2 O 3 Titanium oxide TiO 2 And an oxidizing agent such as hydrogen peroxide H 2 O 2 Potassium permanganate KMnO 4 Potassium periodate KIO 3 And a complexing agent. At present, the oxidant used for preparing the polishing solution is hydrogen peroxide (namely peroxide), but the hydrogen peroxide is unstable and is easy to decompose, so that the CMP rate is unstable, and only the existing preparation is realized. Copper is a corrosion-resistant element and a dielectric layer such as TEOS, siO 2 The hardness of the two materials is different, and the polishing rate of copper is slower than that of the dielectric layer. Over-polishing is often required in the process to completely remove copper, whereby dishing occurs on the surface of the dielectric layer. As the number of layers increases, the superposition of recessed regions becomes more and more severe, so that copper metal residues are generated on the surface of the dielectric layer, resulting in a decrease in circuit reliability. Therefore, in the copper CMP process, not only is the high removal rate required for the polishing slurry required, but also the polishing rate ratio of copper to the dielectric layer is controlled within a reasonable range to achieve balanced polishing and finally achieve global high planarization.
The dishing (dishing) is solved by using a high valence metal compound similar to the wiring metal instead of the conventional use of an oxidizing agent in CMP without adding an oxidizing agent (CN 111826089A) under CMP conditions, such as an inorganic copper salt, an organic copper salt, a cobalt high valence salt or a ruthenium high valence salt. However, the oxidation of the high-valence metal compound of the same metal is insufficient, resulting in a decrease in polishing rate and an increase in polishing time. Therefore, there is a need for improvements in CMP polishing agents, developing a highly efficient polishing liquid for copper interconnect lines and a process for producing the same.
Disclosure of Invention
The invention provides an integrated circuit copper chemical mechanical polishing composition and a preparation process thereof, which are used for solving the problems of dishing caused by unbalanced copper and dielectric layer removal rate in the conventional copper interconnection chemical mechanical polishing process, and low polishing rate caused by insufficient oxidizing property of high-valence metal compounds using the same metal.
The invention provides an integrated circuit copper chemical mechanical polishing composition which comprises the following raw materials in parts by weight: 3 to 5 parts of nano abrasive particles, 0.1 to 5.0 parts of high cerium oxidant, 0.01 to 2.0 parts of metal complexing agent or metal chelating agent and 0.01 to 5.0 parts of surfactant;
the nano grinding particles are composed of silicon oxide and cerium oxide; the mol ratio of the silicon oxide to the cerium oxide is 1:1-5.
Preferably, the granularity of the silicon oxide is 10-160 nm, and the granularity of the cerium oxide is 20-100 nm.
Preferably, the cerium oxide is obtained by calcining basic cerium carbonate at 500-800 ℃ for 6-24 hours, and 2 theta angles of XRD diffraction characteristic peaks of the cerium oxide are 15.9 degrees, 20.2 degrees, 30.2 degrees, 38.1 degrees and 42.8 degrees.
Preferably, the high cerium oxidant is one or a mixture of a plurality of cerous sulfate, cerous nitrate, cerous acetate, ammonium ceric nitrate and ceric hydroxide.
Preferably, the metal complexing agent or metal chelating agent is selected from one or more of glycine, glutamic acid, lysine, tartaric acid, maleic acid, citric acid, oxalic acid, ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetic acid, polyacrylic acid, hydrolyzed polymaleic anhydride, citric acid chelating agent or diethylenetriamine pentaacetic acid.
Preferably, the surfactant is selected from one or a mixture of more of ammonium polyacrylate, polyacrylamide, sodium tripolyphosphate, sodium polyphosphate, polyethylene glycol, polyvinyl alcohol, sodium dodecyl benzene sulfonate, sodium hydrogen phosphate and sodium pyrophosphate.
Preferably, the polishing composition further comprises a pH adjustor selected from one or more of sulfuric acid, nitric acid, hydrochloric acid, acetic acid, ammonium hydroxide, potassium hydroxide, sodium hydroxide, monoethanolamine, diethanolamine, and triethanolamine.
The invention also provides a preparation method of the polishing composition, which comprises the following steps:
weighing nano grinding particles, a high cerium oxidant, a metal complexing agent or a metal chelating agent and a surfactant according to parts by weight;
and (3) sanding and mixing the nano grinding ions and the high cerium oxide, adding the metal complexing agent or the metal chelating agent and the surfactant, adjusting the pH to 1.0-6.0, centrifuging, taking supernatant and grinding.
The invention also provides the use of the polishing composition in planarization of integrated circuit fabrication.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention uses high cerium as oxidant to replace the existing hydrogen peroxide, the high cerium oxidant has higher oxidation performance and better stability, and simultaneously uses silicon oxide and cerium oxide compound as grinding particles, controls the silicon-cerium ratio to balance the grinding rate of the metal layer and the dielectric layer, and solves the problem of dishing caused by unbalanced removal rate of copper and the dielectric layer in the existing copper interconnection chemical mechanical polishing process and the problem of reduction of the grinding rate caused by insufficient oxidizing property of high-valence metal compounds using the same metal.
2. The invention selects the ceric as the oxidant, which not only has higher oxidation effect, but also generates Ce 4+ The ions can enhance the chemical action during polishing (the same as the cerium oxide in the abrasive component) and thus achieve a higher selectivity.
3. The total amount of silica and ceria in the polishing composition is not more than 5%, and particularly between 3% and 5%, is effective in improving polishing efficiency.
4. The complexing agent used in the invention can react with metal ions in the solution to form a stable water-soluble complex. The complex can prevent metal ions from gathering on the surface of the material, promote the decomposition and regeneration of oxide on the surface of the metal, and is beneficial to forward progress of reaction and removal of the material and post-cleaning process.
Drawings
FIG. 1 is a schematic cross-sectional view of an IC circuit;
FIG. 2 shows cerium oxide (CeO) 2 ) XRD pattern;
FIG. 3 shows cerium oxide (CeO) 2 ) A TEM image;
fig. 4 shows a basic cerium carbonate (Ce (CO) 3 ) 2 OH 2 O) XRD pattern.
Detailed Description
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
The purpose of the present invention is to convert the higher hardness metal into a metal oxide that is easier to remove. The oxidizing agent commonly used in the prior art is potassium periodate (KIO) 4 ) Hydrogen peroxide (H) 2 O 2 ) Potassium permanganate (KMnO) 4 ) Etc. H 2 O 2 Is weak in oxidizing property and has a deviation in stability. KMnO in alkaline solution 4 The high-oxidation-resistance polishing agent has high stability and strong oxidizing property, but is dissolved in water to form mauve, and the high oxidizing property of the high-oxidation-resistance polishing agent is extremely easy to damage polishing equipment and polishing pads, so that the later cleaning work is seriously influenced, and the high-oxidation-resistance polishing agent is unfavorable for large-scale industrial application. The invention selects the ceric compound as the oxidant, such as ceric nitrate [ Ce (NO) 3 ) 4 ]Ceric sulfate [ Ce (SO) 4 ) 2 ]Ceric ammonium nitrate [ Ce (NH) 4 ) 2 (NO 3 ) 6 ]Cerium perchlorate [ Ce (ClO) 4 ) 4 ]Cerium hydroxide [ Ce (OH) 4 ]Ceric acetate [ Ce (CH) 3 COO) 4 ]。
Complexing agents useful in the present invention may beWith metal ions in solution (e.g. Ce 3+ 、Cu 2+ 、Co 3+ ) The reaction forms a stable water-soluble complex. The complex can prevent metal ions from gathering on the surface of the material, promote the decomposition and regeneration of oxide on the surface of the metal, and is beneficial to forward progress of reaction and removal of the material and post-cleaning process. Complexing agents which can be used in the invention are disodium ethylenediamine tetraacetate (C 10 H 16 N 2 O 8 Na 2 ) Sodium citrate (C) 6 H 8 O 7 Na), oxalic acid (H 2 O 4 C 2 ) Glycine (C) 2 H 5 NO 2 ) Tartaric acid (C) 4 H 6 O 6 ) Glutamic acid, lysine, citric acid, ethylenediamine tetraacetic acid, polyacrylic acid, hydrolyzed polymaleic anhydride, diethylenetriamine pentaacetic acid.
The pH regulator used in the present invention is selected from acetic acid [ CH ] 3 COOH]Nitric acid (HNO) 3 ) Sulfuric acid (H) 2 SO 4 ) Hydrochloric acid (HCl), monoethanolamine (C) 2 H 7 NO), diethanolamine (C) 4 H 11 NO 2 ) Triethanolamine (C) 6 H 15 NO 3 ) One or more of ammonium hydroxide, potassium hydroxide and sodium hydroxide.
The surfactant is favorable for maintaining the Zeta potential of the system at a higher absolute value, so that the grinding slurry system is stable. The surfactant used in the present invention is an anionic surfactant, a nonionic surfactant, such as sodium or potassium alkylbenzenesulfonate, sodium polyacrylate, polyethylene glycol, polyvinyl alcohol, sodium polyphosphate, sodium tripolyphosphate, polyacrylamide, sodium dodecylbenzenesulfonate, sodium hydrogen phosphate, sodium pyrophosphate, or a mixture of two or more of the above.
The silica sol used in the examples of the present invention is a dispersion of nanoscale silica particles in water or in a solvent.
Example 1
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.1% of ceric sulfate, 0.1% of glycine, 0.1% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 550deg.C for 24 hr, mixing with water to obtain slurry with 5%, and grinding with sand mill to obtain nanometer cerium oxide with particle size of 20nm. The use of cerium hydroxycarbonate can achieve a more consistent crystal structure.
Fig. 2 and 3 are XRD and TEM images of cerium oxide, respectively.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- =Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O=2Ce(OH)CO 3 +CO 2 。
fig. 4 shows a basic cerium carbonate (Ce (CO) 3 ) 2 OH 2 O) XRD pattern.
Cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
Ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - =Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 =2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 =Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: soluble cerium80g/L of salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 1 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 2
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.1% of ceric sulfate, 0.1% of glycine, 0.1% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by regulating soluble cerium salt with deionized water to 30g/L, mixing with precipitant NH at 40deg.C 4 HCO 3 The solution (concentration 10%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- =Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O=2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - =Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 =2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 =Ce(SO) 2 +4H 2 O
The mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 1 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 3
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.1% of ceric sulfate, 0.1% of glycine, 0.1% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 ℃), calcining at 800 deg.C for 6 hr, mixing the calcined product with water to obtain 15% slurry, and grinding with sand mill to obtain nano cerium oxide with particle size of 80nm.
The basic cerium carbonate is prepared by regulating soluble cerium salt with deionized water to 30g/L, mixing with precipitant NH at 40deg.C 4 HCO 3 The solution (concentration 10%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- =Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O=2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - =Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 =2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 =Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
taking silica sol (80 nm, 40%) and nano cerium oxide CeO 2 (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 1 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 4
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.1% of ceric sulfate, 0.1% of glycine, 0.1% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 ℃), calcining at 600deg.C for 6 hr, mixing with water to obtain 10% slurry, and grinding with sand mill to obtain nanometer cerium oxide with particle size of 60nm.
The basic cerium carbonate is prepared by regulating soluble cerium salt with deionized water to 30g/L, mixing with precipitant NH at 40deg.C 4 HCO 3 The solution (concentration 10%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- =Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O=2Ce(OH)CO 3 +CO 2
Cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) The reaction was stirred for 30 minutes to suspendBoiling the solution, standing at room temperature for cooling, washing, and filtering to obtain ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - =Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 =2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 =Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 1 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 5
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.1% of ceric sulfate, 0.1% of glycine, 0.1% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120deg.C), calcining at 800deg.C for 6 hr, mixing the obtained mixture with water to obtain 15% slurry, and grinding with sand mill to obtain nanometer powderCerium oxide, particle size 80nm.
The basic cerium carbonate is prepared by regulating soluble cerium salt with deionized water to 30g/L, mixing with precipitant NH at 40deg.C 4 HCO 3 The solution (concentration 10%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- =Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O=2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, 30% hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - =Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 =2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 =Ce(SO) 2 +4H 2 O
The mass concentration of each substance is as follows: 45g/L of soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 12%, hydrogen peroxide 30% and sulfuric acid 35%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) Glycine, adjusting pH to 5 with 10% nitric acid and 30% triethanolamine, centrifuging the slurry with a centrifuge, collecting supernatantGrinding to obtain the final product. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 6
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.1% of ceric hydroxide, 0.1% of glycine, 0.1% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 550deg.C for 24 hr, mixing with water to obtain slurry with 5%, and grinding with sand mill to obtain nanometer cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration is 30%, W/W) is reacted to obtain a precipitation product, and the precipitation product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- =Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O=2Ce(OH)CO 3 +CO 2
the polishing composition is prepared according to the following method:
the silica sol solution (80 nm, 40%) was mixed with the nano cerium oxide solution (10%), ceric hydroxide and ultrapure water in a mill premix tank. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) Regulating pH to 5 with 10% nitric acid and 30% triethanolamine, centrifuging the slurry with a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, and the pressure is 4psiThe polishing head rotation speed is 120prm, the lower fixed disk rotation speed is 80rpm, the polishing time is 60 seconds, the copper test piece is 40mm x 3mm, the thickness of copper deposited by silicon substrate CVD is 2000nm, and the silicon oxide test piece: PVD deposition of SiO on silicon substrate 2 800nm。
Example 7
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.1% of ceric sulfate, 0.1% of polyacrylic acid, 0.1% of sodium dodecyl benzene sulfonate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- =Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O=2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - =Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 =2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 =Ce(SO) 2 +4H 2 O
The mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And adjusting the pH of the slurry to 1 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 8
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.1% of cerous sulfate, 0.1% of citric acid chelating agent, 0.1% of polyethylene glycol and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- =Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O=2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - =Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 =2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 =Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min by starting a sand mill, adding a citric acid chelating agent and polyethylene glycol into the suspension mixture, adjusting the pH to 1 by using 10% nitric acid and 30% triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 9
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 3% of silicon oxide, 2% of cerium oxide, 0.2% of ceric sulfate, 0.1% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- =Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O=2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - =Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 =2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 =Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 2.5 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 10
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 3% of silicon oxide, 2% of cerium oxide, 0.5% of ceric sulfate, 0.2% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- =Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O=2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) stirringAdding into cerium salt solution under stirring, precipitating completely, and adding hydrogen peroxide (H) 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - =Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 =2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 =Ce(SO) 2 +4H 2 O
The mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 3 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 11
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 3% of silicon oxide, 1% of cerium oxide, 1% of ceric sulfate, 0.3% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) After slurrying with water (S: L=1:2)Ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- =Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O=2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - =Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 =2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 =Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 )、And (3) adjusting the pH of glycine to 3 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 12
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.5% of ceric sulfate, 0.2% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- =Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O=2Ce(OH)CO 3 +CO 2
Cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - =Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 =2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 =Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 4 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 13
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 2% of silicon oxide, 2% of cerium oxide, 0.3% of ceric sulfate, 0.5% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- =Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O=2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - =Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 =2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 =Ce(SO) 2 +4H 2 O
The mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 4.5 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressure is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds,40mm for copper coupon 3mm, 2000nm for CVD deposited copper thickness for silicon substrate, silicon oxide coupon: PVD deposition of SiO on silicon substrate 2 800nm。
Example 14
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 2% of silicon oxide, 2% of cerium oxide, 0.3% of ceric sulfate, 0.2% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- =Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O=2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - =Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 =2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 =Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
taking silica sol (80 nm, 40%) and nano cerium oxide CeO 2 (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) Regulating pH to 6 with 10% nitric acid and 30% triethanolamine, centrifuging the slurry with a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 15
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 4% of cerium oxide, 1% of ceric sulfate, 0.1% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- =Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O=2Ce(OH)CO 3 +CO 2
Cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - =Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 =2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 =Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 5 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Comparative example 1
An integrated circuit copper chemical mechanical polishing composition differs from example 13 only in that the ceric sulfate is replaced with hydrogen peroxide and the pH is adjusted to 4.0 during the preparation process.
Comparative example 2
An integrated circuit copper chemical mechanical polishing composition differing from example 13 in the composition of the raw materials, specifically: 3% of silicon oxide, 2% of cerium oxide, 0.5% of ceric sulfate, 0.2% of hydrogen peroxide, 0.1% of glycine, 0.2% of ammonium polyacrylate and the balance of water. And simultaneously, the pH value is adjusted to 8.5 in the preparation process.
Comparative example 3
An integrated circuit copper chemical mechanical polishing composition differing from example 13 in the composition of the raw materials, specifically: 1% of silicon oxide, 1% of cerium oxide, 1% of ceric sulfate, 0.3% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Comparative example 4
An integrated circuit copper chemical mechanical polishing composition differing from example 13 in the composition of the raw materials, specifically: 3% of silicon oxide, 3% of cerium oxide, 1% of ceric sulfate, 0.3% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Since the effects of the polishing compositions improved in examples 1 to 14 are substantially the same, the effects will be described below by taking only the polishing compositions provided in examples 11 to 16 as examples.
The removal rates of copper and silicon oxide in each of examples 1 to 14 and comparative examples 1 to 3 were measured, and the results are shown in Table 1.
Table 1 removal rates of copper and silicon oxide from each group
As is clear from Table 1, the copper removal rate increased with the increase in the content of cerium oxide, pH and silica sol (examples 11, 12 and 13). The ceric sulfate may replace hydrogen peroxide as an oxidizing agent (comparative example 1). The pH was increased and the oxidation was reduced by partial hydrolysis of the ceric oxide, resulting in a reduced removal rate (comparative example 3). SiO (SiO) 2 ∶CeO 2 The removal rate of copper and silicon oxide is balanced strongly=3:2. The improvement in cerium oxide facilitates the removal of silicon oxide (example 15).
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (9)
1. The integrated circuit copper chemical mechanical polishing composition is characterized by comprising the following raw materials in parts by weight: 3 to 5 parts of nano abrasive particles, 0.1 to 5.0 parts of high cerium oxidant, 0.01 to 2.0 parts of metal complexing agent or metal chelating agent and 0.01 to 5.0 parts of surfactant;
The nano grinding particles consist of silicon oxide and cerium oxide;
the mol ratio of the silicon oxide to the cerium oxide is 1:1-5.
2. The polishing composition of claim 1, wherein the silica has a particle size of 10 to 160nm and the ceria has a particle size of 20 to 100nm.
3. The polishing composition of claim 1, wherein the cerium oxide is a basic cerium carbonate calcined at 500 ℃ to 800 ℃ for 6 to 24 hours, and the 2 theta angles of XRD diffraction characteristic peaks of the cerium oxide are 15.9 °, 20.2 °, 30.2 °, 38.1 °, 42.8 °.
4. The polishing composition of claim 1, wherein the high cerium oxide is one or a mixture of ceric sulfate, ceric nitrate, ceric acetate, ammonium ceric nitrate, or ceric hydroxide.
5. The polishing composition of claim 1, wherein the metal complexing or metal chelating agent is selected from the group consisting of glycine, glutamic acid, lysine, tartaric acid, maleic acid, citric acid, ethylenediamine tetraacetic acid, polyacrylic acid, hydrolyzed polymaleic anhydride, citric acid chelating agent, and mixtures of one or more of diethylenetriamine pentaacetic acid.
6. The polishing composition of claim 1, wherein the surfactant is selected from one or more of ammonium polyacrylate, polyacrylamide, sodium tripolyphosphate, sodium polyphosphate, polyethylene glycol, polyvinyl alcohol, sodium dodecylbenzenesulfonate, sodium hydrogen phosphate, sodium pyrophosphate, and mixtures thereof.
7. The polishing composition of claim 1, further comprising a PH adjustor selected from one or more of sulfuric acid, nitric acid, hydrochloric acid, acetic acid, ammonium hydroxide, potassium hydroxide, sodium hydroxide, monoethanolamine, diethanolamine, and triethanolamine.
8. A method of preparing the polishing composition of claim 7, comprising the steps of:
weighing nano grinding particles, a high cerium oxidant, a metal complexing agent or a metal chelating agent and a surfactant according to parts by weight;
and (3) sanding and mixing the nano grinding ions and the high cerium oxide, adding the metal complexing agent or the metal chelating agent and the surfactant, adjusting the pH to 1.0-6.0, centrifuging, taking supernatant and grinding.
9. Use of the polishing composition of any one of claims 1-7 in planarization of integrated circuit fabrication.
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