WO2008025209A1 - Pâte de polissage pour matériau faiblement diélectrique - Google Patents
Pâte de polissage pour matériau faiblement diélectrique Download PDFInfo
- Publication number
- WO2008025209A1 WO2008025209A1 PCT/CN2007/002102 CN2007002102W WO2008025209A1 WO 2008025209 A1 WO2008025209 A1 WO 2008025209A1 CN 2007002102 W CN2007002102 W CN 2007002102W WO 2008025209 A1 WO2008025209 A1 WO 2008025209A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polishing liquid
- liquid according
- acid
- polishing
- weight
- Prior art date
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 124
- 239000003989 dielectric material Substances 0.000 title claims abstract description 20
- 239000002002 slurry Substances 0.000 title abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000002738 chelating agent Substances 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 58
- 239000002245 particle Substances 0.000 claims description 46
- -1 amine compound Chemical class 0.000 claims description 29
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 25
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 20
- 229920002125 Sokalan® Polymers 0.000 claims description 19
- 239000004584 polyacrylic acid Substances 0.000 claims description 19
- 239000004094 surface-active agent Substances 0.000 claims description 16
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 11
- 235000011187 glycerol Nutrition 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 230000000844 anti-bacterial effect Effects 0.000 claims description 8
- 239000003899 bactericide agent Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 6
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920002307 Dextran Polymers 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 4
- 239000013522 chelant Substances 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- 108010064470 polyaspartate Proteins 0.000 claims description 4
- 229920001529 polyepoxysuccinic acid Polymers 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 3
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- AEDAWHHRIHMZAR-UHFFFAOYSA-N [O-][N+](=O)CN1CCCC1=O Chemical compound [O-][N+](=O)CN1CCCC1=O AEDAWHHRIHMZAR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- JVQIKJMSUIMUDI-UHFFFAOYSA-N 3-pyrroline Chemical compound C1NCC=C1 JVQIKJMSUIMUDI-UHFFFAOYSA-N 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 239000002280 amphoteric surfactant Substances 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 229960003237 betaine Drugs 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- XTOQOJJNGPEPMM-UHFFFAOYSA-N o-(2-oxo-1,3,2$l^{5}-dioxaphosphinan-2-yl)hydroxylamine Chemical compound NOP1(=O)OCCCO1 XTOQOJJNGPEPMM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims description 2
- 150000004291 polyenes Chemical class 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims 1
- UXYAJXBVMZFRMS-UHFFFAOYSA-N 2-hydroxy-1,3,2$l^{5}-dioxaphosphepane 2-oxide Chemical compound OP1(=O)OCCCCO1 UXYAJXBVMZFRMS-UHFFFAOYSA-N 0.000 claims 1
- 229920001661 Chitosan Polymers 0.000 claims 1
- DDAQLPYLBPPPRV-UHFFFAOYSA-N [4-(hydroxymethyl)-2-oxo-1,3,2lambda5-dioxaphosphetan-2-yl] dihydrogen phosphate Chemical compound OCC1OP(=O)(OP(O)(O)=O)O1 DDAQLPYLBPPPRV-UHFFFAOYSA-N 0.000 claims 1
- 229920006243 acrylic copolymer Polymers 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 150000003009 phosphonic acids Chemical class 0.000 claims 1
- JHHZLHWJQPUNKB-UHFFFAOYSA-N pyrrolidin-3-ol Chemical compound OC1CCNC1 JHHZLHWJQPUNKB-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 26
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 24
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 description 20
- 239000004743 Polypropylene Substances 0.000 description 15
- 229920001155 polypropylene Polymers 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 6
- 239000000356 contaminant Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- OPMDOWQLMDOOMW-UHFFFAOYSA-N 1-(2-aminoethylamino)ethane-1,2-diol Chemical compound NCCNC(O)CO OPMDOWQLMDOOMW-UHFFFAOYSA-N 0.000 description 4
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 4
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 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 description 2
- VCTMKGASQVKIQC-UHFFFAOYSA-N 1-(2-chlorotetradecan-2-yl)-2-methylbenzene Chemical compound CCCCCCCCCCCCC(C)(C1=CC=CC=C1C)Cl VCTMKGASQVKIQC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 229940120146 EDTMP Drugs 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- SDOUBTXJBXLRGM-UHFFFAOYSA-N [N+](=O)([O-])CC=1NC=CC=1 Chemical compound [N+](=O)([O-])CC=1NC=CC=1 SDOUBTXJBXLRGM-UHFFFAOYSA-N 0.000 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 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 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 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LMHAGAHDHRQIMB-UHFFFAOYSA-N 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(Cl)C1(F)Cl LMHAGAHDHRQIMB-UHFFFAOYSA-N 0.000 description 1
- FHHPEPGEFKOMOF-UHFFFAOYSA-N 2-hydroxy-1,3,2lambda5-dioxaphosphetane 2-oxide Chemical compound OP1(=O)OCO1 FHHPEPGEFKOMOF-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 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 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- QVKOLZOAOSNSHQ-UHFFFAOYSA-N prop-1-ene;prop-2-enoic acid Chemical compound CC=C.OC(=O)C=C QVKOLZOAOSNSHQ-UHFFFAOYSA-N 0.000 description 1
- QGKLPGKXAVVPOJ-UHFFFAOYSA-N pyrrolidin-3-one Chemical compound O=C1CCNC1 QGKLPGKXAVVPOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- 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
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
-
- 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 present invention relates to a polishing liquid, and more particularly to a polishing liquid for polishing a low dielectric material. Do not
- CMP chemical mechanical polishing
- polishing fluids or polishing slurries abrasive and chemically active solutions
- the CMP polishing liquid mainly includes abrasives, chemicals, solvents, and the like.
- the abrasive is mainly various inorganic or organic particles such as silica, alumina, zirconia, cerium oxide, iron oxide, polymer particles and/or mixtures thereof.
- the solvent of the CMP polishing liquid is mainly water or an alcohol. Chemical reagents are used to control polishing rate and polishing selectivity, improve polishing surface performance, and improve the stability of the polishing solution, including oxidizing agents, complexing agents, corrosion inhibitors, and/or surfactants.
- Ce0 2 is an abrasive particle, and due to the higher hardness, surface scratching is liable to occur.
- USP 6,270,395 discloses the use of carbon, carbides and certain metal oxides as abrasive particles, increasing the likelihood of introduction of surface contaminants.
- the low dielectric material polishing fluids currently in use do not meet manufacturing costs and techniques. The perfect combination of performance, surface finish, polishing selectivity and surface topography control.
- the object of the present invention is to provide a polishing solution of a low dielectric material having a good surface finish in order to solve the problem of lower removal rate of low dielectric material and less controllable polishing selection under lower pressure.
- the polishing liquid of the present invention comprises an abrasive and water, and further comprises one or more metal chelating agents, an azole film former and an oxidizing agent.
- the polishing liquid of the present invention further includes a surfactant.
- the abrasive is SiO 2 sol particles, 810 2 sol particles coated with aluminum or doped aluminum, A 1203 particles, high polymer particles or a mixture thereof.
- the particle size of the particles is preferably 20 to 150 nm;
- the metal chelating agent of the present invention is one or more organic phosphonic acid or polyorganic acid chelate;
- the organic phosphonic acid is: butyl phosphonium 2-phosphate, 2, 4 tricarboxylic acid, hydroxyl hydroxy Ethyl diphosphate, 2-hydroxyphosphonoacetic acid, aminotrimethylenephosphoric acid, diethylenetriamine pentamethylphosphoric acid, ethylenediaminetetramethylenephosphoric acid, polyhydric alcohol phosphate or polyaminopolyether-4 Methylene phosphate;
- the polyorganic acid chelate is polyepoxysuccinic acid, polyaspartic acid, hydrolyzed polymaleic anhydride, polymaleic anhydride-polypropylene An olefinic acid copolymer, an acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, an acrylic acid-hydroxypropyl acrylate copolymer or an acrylic acid-acrylate-phosphoric acid-sulfonate
- the metal chelating agent weight percentage is preferably 0.01 to 2 ° /. ;
- the azole-based film-forming agent of the present invention is benzotriazole and a derivative thereof, 1-phenyl-5-mercapto-tetrazole, 2-mercapto-benzothiazole or 2-mercaptobenzimidazole.
- the concentration of the azole film former is preferably 0.01 to 1% by weight
- the oxidizing agent of the present invention is ⁇ 2 ⁇ 2, persulfuric acid and salts thereof or organic peroxides.
- the oxidant weight percentage concentration is preferably 0 to 10 ° / 0;
- the surfactant according to the present invention is a cationic surfactant, an anionic surfactant, an amphoteric surfactant or a nonionic surfactant; the surfactant is: polyacrylic acid and its salt ( ⁇ ), polyacrylic acid Ammonium, polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyethyleneimine (PEA), quaternary ammonium salt surfactant, betaine, amino acid surfactant, fatty alcohol polyoxyethylene ether, shell polymerization Sugar or dextran.
- polyacrylic acid and its salt ⁇
- polyacrylic acid Ammonium polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyethyleneimine (PEA), quaternary ammonium salt surfactant, betaine, amino acid surfactant, fatty alcohol polyoxyethylene ether, shell polymerization Sugar or dextran.
- the polyacrylic acid and the salt thereof of the present invention have a molecular weight ranging from 2,000 to 300,000, the polyacrylamide has a molecular weight ranging from 1,000 to 5,000,000, the polyethylene glycol has a molecular weight ranging from 200 to 10,000, and the molecular weight of the polyvinyl alcohol.
- the molecular weight range of 1000-100,000 polyethyleneimine is 1000 ⁇ 100,000, and the molecular weight of dextran is 1000-200,000.
- the concentration percentage of the surfactant is preferably 0.01 to 0.5% ;
- the polishing liquid of the present invention further includes one or more of an organic amine compound, a nitrogen heterocyclic compound, glycerin or a bactericide.
- the organic amine compound is a polyene polyamine, a polyhydroxy polyamine, an ethylenediamine or a cyclic amine;
- the nitrogen heterocyclic compound is nitromethylpyrrole, nitromethylpyrrolidone, 3-pyrroline or 3-pyrrolidone.
- the organic amine compound preferably has a concentration by weight of 20 to 1000 ppm;
- the glycerol weight percentage concentration is preferably from 0 to 10%.
- the bactericide is preferably a quaternary ammonium salt.
- the concentration of the bactericide is preferably from 10 to 500 ppm by weight.
- the polishing liquid PH value of the present invention is preferably 8 to 12;
- the polishing liquid of the invention preferred polishing low dielectric material is carbon doped oxide (CDO) low dielectric substrate material comprises BD1 (black diamond 1), BD2 (black diamond 2) or porous material (core materials) 0
- the positive progressive effect of the present invention is that the present invention uses a silica sol particle having a particle size of 20 to 150 nm, and is compatible with the metal chelating agent described in the patent, and is very effective for removing the ruthenium barrier layer and the low dielectric material. , and get better surface roughness, no surface corrosion and surface damage, low surface impurities that can be removed, and the polishing selection ratio can be adjusted according to the needs of different processes to obtain the ideal surface appearance.
- the polishing liquid of the present invention can have a higher removal rate of a low dielectric material and a suitable polishing selection ratio for other materials at a lower pressure, and a polished surface finish is better. It can be used to prevent local and overall corrosion during metal polishing, reduce surface contamination and improve product yield.
- Figure 1 is a SEM image of a surface of a cubic metal copper after polishing with a sol particle using a comparative polishing solution
- 2 is an SEM image of the surface of the metal copper after polishing using the polishing liquid of Example 12.
- FIG. 3 is an SEM image of the thin metal copper wire after polishing with the comparative polishing liquid 1 sol;
- FIG. 4 is a use example. 12 SEM image on the surface of the square metal copper after polishing;
- FIG. 5 is a diagram showing the removal rate of the low dielectric material using the embodiment 5 (changing the pH value) as a function of the pH value of the polishing liquid;
- Figure 6 is a graph showing the change rate of low dielectric material removal rate with oxidant concentration using Example 5 (changing oxidant concentration);
- Figure 7 is a graph showing the rate of removal of low dielectric material with the concentration of the medium chelating agent using Example 6 (changing the concentration of the chelating agent).
- PAPEMP polyaminopolyether tetramethylene phosphonic acid
- PAPEMP polyaminopolyether tetramethylene phosphonic acid
- PDA polyethyleneimine
- PAPEMP polyamino polyether tetramethylene phosphonic acid
- CTAB cetyltrimethylammonium bromide
- Polishing solution 17 aluminum miscellaneous silica (45nm) 10%, BTA 0.1%, polyaminopolyether tetramethylene phosphonic acid (PAPEMP) 0.2%, H2O2 1.5%, polyacrylic acid or polypropylene salt (molecular weight 5000) (PAA) 0.2% and water balance, pE ll;
- PAPEMP polyaminopolyether tetramethylene phosphonic acid
- PAA polyacrylic acid or polypropylene salt
- PAPEMP polyaminopolyether tetramethylene phosphonic acid
- Preparation method of polishing solution Add a certain amount of silica sol to the stirrer, mix and add deionized water at a certain rate, mix well, add 50% glycerin aqueous solution, stir and hook, add 1% BTA aqueous solution, stir evenly. Then, an organic acid, an aqueous solution of an surfactant, and an optional component such as an organic amine and a bactericide are added, and then adjusted to a desired pH with a KOH (50%) solution to obtain a polishing liquid.
- Polishing material BD (low-k material), TEOS, Ta, Cu; polishing conditions: l ⁇ 1.5Psi, polishing disc and polishing head speed 70/90rpm, polishing pad Politex, polishing fluid flow rate 100ml/min, Logitech PM5 Polisher, After polishing, use DIW and cleaning solution and then DIW cleaning procedure.
- Polishing solution 20 SiO 2 sol particles (80 nm) used in the patent 10%, 1-phenyl-5-mercapto-tetrazole (PMTA) 0.5%, polyaminopolyether tetramethylene phosphonic acid (PAPE P) 0.1%, 3% persulfate, polyacrylic acid or polypropylene salt (molecular weight 5000) (PAA) 0.01% and water balance, pH 11.5;
- PMTA 1-phenyl-5-mercapto-tetrazole
- PAPE P polyaminopolyether tetramethylene phosphonic acid
- PAA polyacrylic acid or polypropylene salt
- ATA 5-amino-1-H-tetrazole
- PAPEMP polyaminopolyether tetramethylene phosphonic acid
- PAPEMP polyaminopolyether tetramethylene phosphonic acid
- PAPEMP polyaminopolyether tetramethylene phosphonic acid
- PAPEMP polyaminopolyether tetramethylene phosphonic acid
- Silica sol particles (20nm) 10%, BTA O.15% used in the polishing liquid 28 patent.
- Polyaminopolyether tetramethylene phosphonic acid (PAPEMP) 0.05%, persulfate 10%, acrylic acid-2- Acrylamide-2-methylpropanesulfonic acid copolymer (molecular weight 5000) 0.2%, glycerin 2%, 1,2-dihydroxyethylethylenediamine 1000 ppm, bactericide (dimethyl dodecyl benzyl chloride) Base ammonium) 100ppm, nitromethylpyrrolidone 1% and water balance, pH 9 ;
- Reference particle sol. BD black diamond doped silicon oxide
- TEOS silicon oxide
- Ta metal germanium-barrier metal material
- Cu metallic copper
- Def surface contaminant
- DSH butterfly recess size
- the SiO 2 sol particles used in the patent have a higher removal rate of low dielectric material than the reference sol particles. Due to the addition of the chelate, the removal rate of the low dielectric material (BD) can be increased to varying degrees. The effect of different addition amounts and different types is shown in Fig. 7. The organic amine compound can be changed even if the amount of addition is small. Metal copper removal rate. The effect of the concentration of hydrogen peroxide is shown in Fig. 6. As shown in Fig. 5, the removal rate of various substrate materials can be changed according to the change of the pH of the polishing liquid, thereby changing the polishing selection ratio to achieve the correction of the surface morphology, and in addition, the surfactant The addition also reduces the amount of surface contaminants and improves surface finish.
- the raw materials and reagents used in the present invention are all commercially available products.
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Description
用于抛光低介电材料的抛光液 技术领域
本发明涉及一种抛光液, 尤其涉及一种用于抛光低介电材料的抛光液。 不
在集成电路制造中, 互连技术的标准在提高, 一层上面又沉积一层, 使 得在衬底表面形成了不规则的形貌。现有技术中使用的一种平坦化方法就是 化学机械抛光(CMP), CMP工艺就是使用一种含磨料的混合物和抛光垫去 抛光一集成电路表面。在典型的化学机械抛光方法中, 将衬底直接与旋转抛 光垫接触, 用一载重物在衬底背面施加压力。 在拋光期间, 垫片和操作台旋 转, 同时在衬底背面保持向下的力, 将磨料和化学活性溶液(通常称为抛光 液或抛光浆料)涂于垫片上, 该抛光液与正在抛光的薄膜发生化学反应开始 进行抛光过程。
CMP抛光液主要包括磨料、 化学试剂和溶剂等。 磨料主要为各种无机 或有机颗粒, 如二氧化硅、 氧化铝、 二氧化锆、 氧化铈、 氧化铁、 聚合物颗 粒和 /或它们的混合物等。 CMP抛光液的溶剂主要为水或醇类。 而化学试剂 是用来控制抛光速率和抛光选择比、改善抛光表面性能以及提高抛光液的稳 定性, 包括氧化剂、 络合剂、 缓蚀剂和 /或表面活性剂等。
传统绝缘材料(TEOS) 由于具有较高的介电常数(3.9 or higher)会导 致传导层之间电容增大, 从而影响集成电路的速度, 使降低效率, 随着集成 电路的复杂化和精细化, 这种基底材料越发不能满足更先进制程的 (65nm 或 45nm)技术要求, 在衬底中引入低介电材料是集成电路技术发展的必然
趋势,随之产生了许多用于低介电材料(CDO)的拋光浆液,如 USP 6,046,112 公开了采用 Zr02为磨料, 配合季铵碱, 生产成本高, USP6,043,155公开了 采用价格较高的 Ce02为磨料粒子, 而且由于硬度更高, 容易产生表面划伤。 USP6,270,395公开了采用碳,碳化物以及某些金属氧化物为磨料颗粒, 增大 了引入表面污染物的可能性, 总之, 目前在用的低介电材料抛光液都没有达 到制造成本和技术表现的完美结合, 普遍存在着表面光洁度,抛光选择性以 及表面形貌控制等方面的问题。
发明概要
本发明的目的是为了解决较低的压力下,低介电材料的去除速率较低及 抛光选择比较难控制的问题, 提供一种表面光洁度好的低介电材料的抛光 液。
本发明的上述目的通过下列技术方案来实现:本发明的抛光液包括磨料 和水, 还包括一种或多种金属螯合剂、 唑类成膜剂和氧化剂。
本发明抛光液还包括表面活性剂。
在本发明中, 所述的磨料为 Si02溶胶颗粒、 覆盖铝或掺杂铝的 8102溶 胶颗粒, A1203颗粒、 高聚物颗粒或者它们的混合物。
所述的颗粒的粒径较佳地是 20〜150nm;
更佳地是 50〜120nm。
本发明所述的金属螯合剂为一种或多种有机膦酸或聚有机酸螯合物;所 述的有机膦酸为: 2-磷酸丁垸 -1, 2, 4三羧酸、 羟基亚乙基二磷酸、 2—羟 基膦酰基乙酸、 氨基三亚甲基磷酸、 二亚乙基三胺五亚甲基磷酸、 乙二胺四 亚甲基磷酸、多元醇磷酸酯或多氨基多醚基四亚甲基磷酸; 所述的聚有机酸 螯合物为聚环氧琥珀酸、 聚天冬氨酸、 水解聚马来酸酐、 聚马来酸酐 -聚丙
烯酸共聚物、 丙烯酸 -2-丙烯酰胺 -2-甲基丙磺酸共聚物、 丙烯酸 -丙烯酸羟丙 酯共聚物或丙烯酸 -丙烯酸酯-磷酸-磺酸盐共聚物。
所述的金属螯合剂重量百分比浓度较佳地为 0.01〜2°/。;
更佳地为 0.1〜1%。
本发明所述的唑类成膜剂为苯并三氮唑及其衍生物、 1-苯基 -5-巯基-四 氮唑、 2-巯基 -苯并噻唑或 2-巯基苯并咪唑。
所述的唑类成膜剂重量百分比浓度较佳地为 0.01〜 1%;
更佳地为 0.1〜0.5%。
本发明所述的氧化剂为 Η2θ2、 过硫酸及其盐或有机过氧化物。
所述的氧化剂重量百分比浓度较佳地为 0〜10°/0;
更佳地为 0.1〜3%。
本发明所述的表面活性剂为阳离子表面活性剂、 阴离子表面活性剂、两 性表面活性剂或非离子表面活性剂; 所述的表面活性剂为: 聚丙烯酸及其盐 (ΡΑΑ)、聚丙烯酰铵、聚乙二醇(PEG)、聚乙烯醇(PVA)、聚乙烯亚胺 (PEA)、 季铵盐表面活性剂、 甜菜碱、 氨基酸型表面活性剂、 脂肪醇聚氧乙烯醚、 壳 聚糖或葡聚糖。
本发明所述的聚丙烯酸及其盐的分子量范围为 2000〜30万, 聚丙烯酰 铵的分子量范围为 1000-500万, 聚乙二醇的分子量范围为 200〜10000, 聚 乙烯醇的分子量范围为 1000-10万, 聚乙烯亚胺的分子量范围为 1000〜10 万, 葡聚糖的分子量范围为 1000-20万。
所述的表面活性剂重量百分比浓度较佳地为 0.01〜0.5%;
更佳地为 0.05〜0.2%。 .
本发明抛光液还包括有机胺类化合物、氮杂环类化合物、甘油或杀菌剂 中的一种或多种。
所述的有机胺类化合物为多烯多胺、 多羟基多胺、 乙二胺或环胺; 所述
的氮杂环类化合物为氮甲基吡咯、氮甲基吡咯烷酮、 3-吡咯啉或 3-吡咯垸醇。 所述的有机胺类化合物重量百分比浓度较佳地为 20〜1000ppm;
更佳地为 50〜500ppm。
所述的甘油重量百分比浓度较佳地为 0〜10%。
所述的杀菌剂较佳地为季铵盐类。
所述的杀菌剂重量百分比浓度较佳地为 10〜500ppm。
本发明抛光液 PH值较佳地为 8〜12;
更佳地为 10.5〜11.5。
本发明的抛光液较佳的抛光低介电材料为掺杂碳的氧化物 (CDO)低介 电基底材料包括 BD1 (black diamond 1)、 BD2(black diamond 2)或多孔材料 (core materials )0
本发明的积极进步效果在于:本发明使用一种颗粒尺寸在 20〜150nm之 间的二氧化硅溶胶颗粒,配合专利中所述的金属螯合剂, 非常有效的去除钽 阻挡层和低介电材料, 并获较好的表面粗糙度, 无表面腐蚀和表面画伤, 较 低可清除的表面污染物, 并可根据不同工艺的需求调整抛光选择比, 获得理 想的表面型貌。
并且本发明的抛光液能在较低的压力下具有较高的低介电材料的去除 速率以及对其它材料的合适的抛光选择比, 抛光后的表面光洁度较好。 能用 于防止金属抛光过程中产生的局部和整体腐蚀,减少表面污染物, 提高产品 良率。
附图说明
图 1为使用对比抛光液 1 .溶胶颗粒拋光后的方块金属铜表面上的 SEM 图;
图 2为使用实施例 12抛光液抛光后的方块金属铜表面上的 SEM图; 图 3为使用对比抛光液 1溶胶騵粒抛光后的细金属铜线上的 SEM图; 图 4为使用实施例 12抛光液抛光后的方块金属铜表面上的 SEM图; 图 5为使用实施例 5(改变 PH值)的低介电材料去除速率随抛光液 PH值 变化情况图;
图 6为使用实施例 5(改变氧化剂浓度)的低介电材料去除速率随氧化剂 浓度变化情况图;
图 7为使用实施例 6 (改变螯合剂浓度) 的低介电材料去除速率随中螯 合剂浓度变化情况图。
发明内容
实施例 1
对比抛光液 1 对比的普通硅溶胶颗粒 (70nm) 10%和水余量, pH=ll ; 抛光液 1 专利中使用的硅溶胶颗粒 (lOOnm) 10%和水余量, pH=ll ; 抛光液 2专利中使用的硅溶胶颗粒 (lOOnm) 5%、 BTA 0.1%、 多氨基多 醚基四亚甲基膦酸 (PAPEMP) 0.2%、 Η2θ2 1.5%和水余量, ρΗ=11 ;
抛光液 3 专利中使用的硅溶胶颗粒 (lOOnm) 10%、 BTA 0.1%、 多氨基 多醚基四亚甲基膦酸(PAPEMP) 0.2%、 Η2θ2 ΐ.5%和水余量, ρΗ=11 ; 抛光液 4 专利中使用的硅溶胶颗粒 (lOOnm) 10%、 BTA 0.1%、 多氨基 多醚基四亚甲基膦酸(PAPEMP) 0.2°/。、 Η2θ2 ΐ.5%、 聚丙烯酸或聚丙烯盐 (分子量为 5000) (ΡΑΑ) 0.2%和水余量, ρΗ=11 ;
抛光液 5 专利中使用的硅溶胶颗粒 (lOOnm) 10%、 BTA 0.1%、 多氨基 多醚基四亚甲基膦酸(PAPEMP) 0.2%、 Η2θ2 ΐ.5%、 聚丙烯酸或聚丙烯盐 (分子量为 5000), (ΡΑΑ) 0.2%、 DEA200ppm和水余量, pH=ll ;
抛光液 6 专利中使用的硅溶胶颗粒 (100nm)10%、 BTA 0.1%、 2-膦酸 丁烷 -1, 2, 4三羧酸 (PBTCA) 0.2%、 H2O2 1.5%、 聚丙烯酸或聚丙烯盐 (分子量为 5000) (PAA) 0.2%和水余量, H=ll ;
拋光液 7 专利中使用的硅溶胶颗粒 (lOOnm) 10°/。、 BTA 0.1%、 羟基亚 乙基二膦酸 (HEDP) 0.2%、 Η2θ2 1.5%、 聚丙烯酸或聚丙烯盐(分子暈为 5000) (ΡΑΑ) 0.2%和水余量, ρΗ=11 ;
抛光液 8 专利中使用的硅溶胶颗粒 (100nm)10%、 BTA 0.1%、氨基三亚 甲基膦酸 (ATMP) 0.2%、 H2O2 1.5%、聚丙烯酸或聚丙烯盐(分子量为 5000) (ΡΑΑ) 0.2%和水余量, ρΗ=11 ;
抛光液 9 专利中使用的硅溶胶颗粒 (lOOnm) 10%、 ΒΤΑ 0.1%、 乙二胺 四亚甲基膦酸 (EDTMPA) 0.2%、 Η2θ2 ΐ.5%、 聚丙烯酸或聚丙烯盐 (分子 量为 5000) (ΡΑΑ) 0.2%和水余量, ρΗ=11 ;
抛光液 10 专利中使用的硅溶胶颗粒 (100nm) 10%、 BTA 0.1%、聚环氧 琥珀酸(PESA) 0.2%、 Η2θ2 ΐ.5%、聚丙烯酸或聚丙烯盐(分子量为 5000) (ΡΑΑ) 0.2%和水余量, ρΗ=11 ;
抛光液 11 专利中使用的硅溶胶颗粒 (100nm) 10%、 BTA 0.1%、 聚天冬 氨酸(PASP) 0.2°/。、 H2O2 1.5%、 聚丙烯酸或聚丙烯盐(分子量为 5000) (ΡΑΑ) 0.2%和水余量, ρΗ=10.9;
抛光液 12 专利中使用的硅溶胶颗粒 (100nm)10%、 BTA 0.1%、 多氨基 多醚基四亚甲基膦酸 (PAPEMP) 0.2%、 H2〇2 l.5%、 聚乙烯亚胺(分子量 为 4000) (PEA) 0.02%和水余量, pH=10,8;
抛光液 13 专利中使用的硅溶胶颗粒 (100nm) 10%、 BTA 0.1°/。、 多氨基 多醚基四亚甲基膦酸 (PAPEMP) 0.05%、 十六烷基三甲基溴化铵(CTAB) 0.1%和水余量, pH=ll ;
抛光液 14 专利中使用的硅溶胶颗粒 (100nm)10%、 BTA 0.1%、 多氨基
多醚基四亚甲基膦酸(PAPEMP)0.2%、辛基酚聚氧乙烯醚(triton 100) 0.05% 和水余量, pH=ll ; '
抛光液 15 Al2O3(100nm)10% BTA 0.1%、多氨基多醚基四亚甲基膦酸 (PAPEMP) 0.2%、 H2O2 1.5%、 聚丙烯酸或聚丙烯盐 (分子量为 5000) (ΡΑΑ) 0.2%和水余量, ρΗ=11 ;
抛光液 16 Al-Covered(45nm)10%> BTA 0.1%, 多氨基多醚棊四亚甲基 膦酸(PAPEMP) 0.2%、 H2O2 1.5%、聚丙烯酸或聚丙烯盐(分子量为 5000) (PAA) . 0.2%和水余量, pH=ll ;
抛光液 17铝惨杂的二氧化硅 (45nm)10%、 BTA 0.1%、 多氨基多醚基四 亚甲基膦酸(PAPEMP) 0.2%、 H2O2 1.5%、 聚丙烯酸或聚丙烯盐 (分子量 为 5000) (PAA) 0.2%和水余量, pE ll ;
抛光液 18 专利中使用的 Si02 10%、 BTA 0.2%、 多氨基多醚基四亚甲 基膦酸 (PAPEMP) 0.2%、丙烯酸 -2-丙烯酰胺 -2-甲基丙磺酸共聚物(分子量 为 5000) 0.2%、 ¾02 1.5%和水余量, PH=11 ;
抛光液制备方法: 将一定量硅溶胶加入搅拌器, 搅拌下以一定速率定量 加入去离子水混合均匀, 再加入 50%甘油水溶液, 搅拌均勾, 加入 1%BTA 水溶液, 搅拌均匀。 然后加入有机酸, 表面活性剂水溶液, 以及有机胺和杀 菌剂等非必要组分, 后用 KOH (50%)溶液调节至所需 PH值即得拋光液。
抛光材料: BD (low-k material), TEOS, Ta, Cu;抛光条件: l〜1.5Psi, 抛光盘及抛光头转速 70/90rpm, 抛光垫 Politex, 拋光液流速 100ml/min, Logitech PM5 Polisher, 抛光后采用 DIW和清洗液而后 DIW清洗程序。
实施例 2
抛光液 19 铝掺杂的氧化硅颗粒 (45nm)10%、 1-苯基 -5-巯基-四氮唑 (PMTA)0.01%、多氨基多醚基四亚甲基膦酸 (PAPEMP) 0.01%、过硫酸 0.1%、
聚丙烯酸或聚丙烯盐 (分子量为 5000) 0.5%和水余量, pH=10.5;
实施例 3
抛光液 20 专利中使用的 Si02溶胶颗粒 (80nm)10%、 1-苯基 -5-巯基-四 氮唑 (PMTA)0.5%、 多氨基多醚基四亚甲基膦酸(PAPE P) 0.1%、 过硫酸 3%、 聚丙烯酸或聚丙烯盐 (分子量为 5000 ) (PAA) 0.01%和水余量, pH=11.5;
实施例 4
抛光液 21 专利中使用的二氧化硅溶胶颗粒 (80nm)10%、 5-氨基 -1-H- 四氮唑 (ATA) 1%、 多氨基多醚基四亚甲基膦酸 (PAPEMP) 2%、 过硫 酸 10%、 聚丙烯酰铵 (分子量为 5000) 0.05%和水余量, pH=12;
实施例 5
抛光液 22专利中使用的二氧化硅溶胶颗粒 (80nm)10%、 2-巯基-苯并噻 唑 0.01%、多氨基多醚基四亚甲基膦酸 (PAPEMP) 0.01%、过硫酸铵 10%、 聚乙烯亚胺 (分子量为 5000) 0.1%和水余量, pH=8;
实施例 6
抛光液 23专利中使用的二氧化硅溶胶颗粒(50nm)10%、 2-巯基苯并咪 唑 0.1%、 多氨基多醚基四亚甲基膦酸(PAPEMP) 0.1%、 过硫酸铵 10%、 聚丙烯酸或聚丙烯盐 (分子量为 5000) (PAA) 0.1%、 甘油 5%、 乙二胺 20ppm、 氯化二甲基十二烷基苄基铵 lOppm和水余暈, pH=ll ;
实施例 7
抛光液 24 专利中使用的二氧化硅溶胶颗粒(50nm)10%、 5-氨基 -1-H- 四氮唑 (ATA) 0. 5%、 多氨基多醚基四亚甲基膦酸(PAPEMP) 1%、 过 硫酸 3%、聚乙二醇(分子量为 400) (PAA) 0.01%、甘油 10%、 氮甲基吡 咯 500ppm、 氯化二甲基十二烷基苄基铵 500ppm和水余量, pH=ll ; .
抛光液 25 专利中使用的二氧化硅溶胶颗粒 (150nm) 10%、 BTA O.15%, 多氨基多醚基四亚甲基膦酸 (PAPEMP) 0.05%、 过硫酸铵 2%、 辛棊酚聚 氧乙烯醚(分子量为 5000) 0.05%、甘油 2%、 1, 2-二羟乙基乙二胺 20ppm、 氯化二甲基十二烷基苄基铵 100ppm、 水余量、 pH=ll ;
实施例 9
抛光液 26 专利中使用的二氧化硅溶胶颗粒(20nm)10%、 BTA 0.15%、 多氨基多醚基四亚甲基膦酸(PAPEMP) 0.05%、过氧乙酸 10%、丙烯酸 -2- 丙烯酰胺 -2-甲基丙磺酸共聚物(分子量为 5000) 0.5%、 甘油 2%、 1, 2- 二羟乙基乙二胺 500ppm、 氯化二甲基十二垸基苄基铵 lOOppm和水余量, pH=ll ;
实施例 10
抛光液 27 专利中使用的二氧化硅溶胶颗粒(20nm)10%、 BTA O.15%, 多氨基多醚基四亚甲基膦酸 (PAPEMP) 0.05%、 过硫酸 10%、 丙烯酸 -2- 丙烯酰胺 -2-甲基丙磺酸共聚物 (分子量为 5000) 0.2%、 甘油 2%、 1, 2- 二羟乙基乙二胺 1000ppm、 杀菌剂(氯化二甲基十二烷基苄基铵) lOOppm 和水余量, pH=9;
实施例 11 '
抛光液 28 专利中使用的二氧化硅溶胶颗粒(20nm)10%、 BTA O.15%. 多氨基多醚基四亚甲基膦酸 (PAPEMP) 0.05%、 过硫酸 10%、 丙烯酸 -2- 丙烯酰胺 -2-甲基丙磺酸共聚物(分子量为 5000) 0.2%、 甘油 2%、 1, 2- 二羟乙基乙二胺 1000ppm、杀菌剂(氯化二甲基十二烷基苄基铵) 100ppm、 氮甲基吡咯烷酮 1%和水余量, pH=9;
实施例 12
低介电材料 BD惨杂碳的氧化硅 (BD1 )及其它基底材料的抛光速率以 及表面污染物和表面形貌特性
抛光液 BD Ta Cu 表面污染 碟型凹陷
(A/min) (A/min) (A/min) 物数量 大小
1* 551 289 220 422 较低 ' 大
1 693 462 156.5 233 较低 大
2 614 350 206 326 较低 较小
3 898 541 257 482 低 较小
4 854 561 271 624 伥 小
5 877 549 179 733 低 大 .
6 887 574 336 653 低 小
7 867 594 288 625 低 大
8 1014 546 350 616 低 凸出
9 840 545 180 659 低 小
10 805 63 〇34 · 342 709 低 小
11 969 559 367 573 低 凸出
12 793 573 335 545 低 小
13 660 795 552 653 低 小'
14 250 538 406 361 低 小
15 274 246 394 440 低 小
16 332 245 423 502 低 小
17 470 442 335 569 低 小
18 1035 564 370 585 低 凸出
1*: 为参照物溶胶颗粒。 BD: black diamond掺杂碳的氧化硅, TEOS: 氧化硅, Ta: 金属钽-阻挡层 金属材料, Cu: 金属铜; Def:表面污染物情况、 DSH: 蝶型凹陷大小,
效果实施例
专利中使用的 Si02溶胶颗粒具有较参照物溶胶颗粒更高的低介电材料 去除速率。 由于螯合物的加入, 可以不同程度地增加低介电材料 (BD) 的 去除速率, 不同的添加量和不同种类的影响在图 7显示, 有机胺类化合物即 使微小的添加量即可明显改变金属铜的去除速率。 双氧水的浓度影响在图 6 中显示, 如图 5中显示随抛光液 PH的变化可以改变各种基底材料的去除速 率, 从而改变抛光选择比, 来达到对表面形貌的矫正, 此外表面活性剂的加 入也可减少表面污染物的数量, 改善表面光洁度。 固含量也是影响 BD去除 速率的重要因素, 固含量增加, 两者的抛光选择比也增加。合适的抛光选择 比可以获得比较好的表面形貌, 凹陷较低。 总之, 通过调节固含量以及各种 组分的相对含量可以调整抛光选择比, 改善表面污染物的情况。来满足不同 制程的技术需求。 所有这些的数据均在较低的下压力下取得 (DF=1.5Psi)。
本发明所使用的原料和试剂均为市售产品。
Claims
1、 一种用于抛光低介电材料的抛光液, 该抛光液包括磨料和水, 其特 征在于: 还包括一种或多种金属螯合剂、 唑类成膜剂和氧化剂。
2、 如权利要求 1所述的抛光液, 其特征在于: 所述的抛光液还包括表 面活性剂。
3、 如权利要求 1所述的拋光液, 其特征在于: 所述的磨料为 Si02溶胶 颗粒、 覆盖铝或掺杂铝的 Si02溶胶颗粒、 A1203颗粒、 高聚物颗粒或它们的 混合物。
4、如权利要求 3所述的抛光液,其特征在于:所述的磨料的粒径是 20〜 150nm。
5、如权利要求 4所述的拋光液,其特征在于:所述的磨料的粒径是 50〜 120nmo
6、 如权利要求 1所述的拋光液, 其特征在于: 所述的金属螯合剂为一 种或多种有机膦酸或聚有机酸螯合物。
7、 如权利要求 6所述的抛光液, 其特征在于: 所述的有机膦酸为: 2- 磷酸丁烷 -1, 2, 4三羧酸、 羟基亚乙基二磷酸、 2—羟基膦酰基乙酸、 氨基 三亚甲基磷酸、 二亚乙基三胺五亚甲基磷酸、 乙二胺四亚甲基磷酸、 多元醇 磷酸酯或多氨基多醚基四亚甲基磷酸。
8、 如权利要求 6所述的抛光液, 其特征在于: 所述的聚有机酸螯合物 为聚环氧琥珀酸、 聚天冬氨酸、 水解聚马来酸酐、 聚马来酸酐 -聚丙烯酸共 聚物、 丙烯酸 -2-丙烯酰胺 -2-甲基丙磺酸共聚物、 丙烯酸 -丙烯酸羟丙酯共聚 物或丙烯酸 -丙烯酸酯-磷酸-磺酸盐共聚物。
9、 如权利要求 6所述的抛光液, 其特征在于: 所述的金属螯合剂重量 百分比浓度为 0.01〜2%。
10、 如权利要求 9所述的抛光液, 其特征在于: 所述的金属螯合剂重量 百分比浓度为 0.1〜1%。
11、 如权利要求 1所述的抛光液, 其特征在于: 所述的唑类成膜剂包括 苯并三氮唑及其衍生物、 1-苯基 -5-巯基-四氮唑、 2-巯基 -苯并噻唑、 苯并咪. 唑或 2-巯基苯并咪唑。
12、 如权利要求 11所述的抛光液, 其特征在于: 所述的唑类成膜剂重 量百分比浓度为 0.01〜1%。
13、 如权利要求 12所述的抛光液, 其特征在于: 所述的唑类成膜剂重 量百分比浓度为 0.1〜0.5%。
14、 如权利要求 1所述的抛光液, 其特征在于: 所述的氧化剂为 Η2θ2、 过硫酸及其盐或有机过氧化物。
15、 如权利要求 14所述的抛光液, 其特征在于: 所述的氧化剂重量百 分比浓度为 0〜: 10%。
16、 如权利要求 15所述的抛光液, 其特征在于: 所述的氧化剂重量百 分比浓度为 0.1〜3%。
17、如权利要求 2所述的抛光液, 其特征在于: 所述的表面活性剂为阳 离子表面活性剂、阴离子表面活性剂、两性表面活性剂或非离子表面活性剂。
18、 如权利要求 17所述的拋光液, 其特征在于: 所述的表面活性剂为: 聚丙烯酸及其盐、 聚丙烯酰铵、 聚乙二醇、 聚乙烯醇、 聚乙烯亚胺、 季铵盐 表面活性剂、 甜菜碱、 氨基酸型表面活性剂、 脂肪醇聚氧乙烯醚、 葡聚糖或 壳聚糖。
19、 如权利要求 17所述的拋光液, 其特征在于: 所述的表面活性剂重 量百分比浓度为 0.01〜0.5%。
20、 如权利要求 19所述的抛光液, 其特征在于: 所述的表面活性剂重 量百分比浓度为 0.05〜0.2°/0。
21、 如权利要求 18所述的抛光液, 其特征在于: 所述的聚丙烯酸及其 盐的分子量范围为 2000〜30万, 聚丙烯酰铵的分子量范围为 1000-500万, 聚乙二醇的分子量范围为 200〜10000,聚乙烯醇的分子量范围为 1000-10万, 聚乙烯亚胺的分子量 ¾围为 1000〜10万, 葡聚糖的分子量范围为 1000-20 万。
22、 如权利要求 1至 21任一项所述的抛光液, 其特征在于: 所述的抛 光液还包括有机胺类化合物、氮杂环类化合物、甘油或杀菌剂中的一种或多 种。
23、 如权利要求 22所述的抛光液, 其特征在于: 所述的有机胺类化合 物为多烯多胺、 多羟基多胺、 乙二胺或环胺; 所述氮杂环类化合物为氮甲基 吡咯、 氮甲基吡咯烷酮、 3-吡咯啉或 3-吡咯烷醇等。
24、 如权利要求 23所述的抛光液, 其特征在于: 所述的有机胺类化合 物重量百分比浓度为 20〜1000ppm。
25、 如权利要求 24所述的抛光液, 其特征在于: 所述的有机胺类化合 物重量百分比浓度为 50〜500ppm。
26、 如权利要求 22所述的抛光液, 其特征在于: 所述的甘油重量百分 比浓度为 0〜10%。
27、 如权利要求 22所述的抛光液, 其特征在于: 所述的杀菌剂为季铵 盐类。
28、 如权利要求 27所述的抛光液, 其特征在于: 所述的杀菌剂重量百 分比浓度为 10〜500ppm。
29、 如权利要求 1至 21任一项所述的抛光液, 其特征在于: 所述的抛 光液 PH值为 8〜12。
30、如权利要求 29所述的抛光液,其特征在于:所述的抛光液 PH值为
10.5〜11.5。
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US7022255B2 (en) * | 2003-10-10 | 2006-04-04 | Dupont Air Products Nanomaterials Llc | Chemical-mechanical planarization composition with nitrogen containing polymer and method for use |
-
2006
- 2006-08-25 CN CNA2006100304572A patent/CN101130665A/zh active Pending
-
2007
- 2007-07-09 WO PCT/CN2007/002102 patent/WO2008025209A1/zh active Search and Examination
- 2007-07-09 CN CN2007800271849A patent/CN101490192B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6852632B2 (en) * | 1999-08-13 | 2005-02-08 | Cabot Microelectronics Corporation | Method of polishing a multi-layer substrate |
US7022255B2 (en) * | 2003-10-10 | 2006-04-04 | Dupont Air Products Nanomaterials Llc | Chemical-mechanical planarization composition with nitrogen containing polymer and method for use |
WO2006028759A2 (en) * | 2004-09-08 | 2006-03-16 | Praxair S. T. Technology, Inc | Aqueous slurry containing metallate-modified silica particles |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI573847B (zh) * | 2010-10-22 | 2017-03-11 | Chemical mechanical polishing liquid (a) | |
CN103820079A (zh) * | 2014-02-21 | 2014-05-28 | 无锡研奥电子科技有限公司 | 用于氮化镓材料的研磨组合物及其制备方法 |
CN106830378A (zh) * | 2017-02-23 | 2017-06-13 | 山东化友水处理技术有限公司 | 一种灰水阻垢剂及其制备和筛选测试方法 |
Also Published As
Publication number | Publication date |
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CN101490192A (zh) | 2009-07-22 |
CN101130665A (zh) | 2008-02-27 |
CN101490192B (zh) | 2012-09-19 |
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